Nitro schiff base metal complex dyes and their use in optical layers for optical data recording
Abstract
The present invention relates to Nitro Schiff base metal complex dyes and their use in optical layers for optical data recording, preferably for optical data recording using a laser with a wavelength up to 450 nm. The invention further relates to a write once read many (WORM) type optical data recording medium capable of recording and reproducing information with radiation of blue laser, which employs Nitro Schiff base metal complex dyes in the optical layer.
Term
Projected expiry 13 November 2026.
- Priority and filed
- Published
- Today
- Projected expiry
19 claims: 5 independent, 14 dependent
- 1A compound of formula (I), wherein M is a divalent metal atom or oxidized divalent metal atom;G1 is a group of formula (II) or of formula (III);R 80 , R 81 , R 82 and R 83 are independently from each other C 1-8 alkyl or C 3-8 cycloalkyl;or R 80 and R 81 together with the C atom to which they are connected according to formula (I), or, independently from R 80 and R 81 , R 82 and R 83 together with the C atom to which they are connected according to formula (II), form a five or six membered aromatic or heteroaromatic cycle, the heteroaromatic cycle containing 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S;the aromatic or heteroaromatic cycle or the C 3-8 cycloalkyl can be annealed with a five or six membered aromatic or heteroaromatic cycle, this second heteroaromatic cycle containing 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S;the C 1-8 alkyl chains, the C 3-8 cycloalkyl, the aromatic or the heteroaromatic cycles can be substituted by 1 to 8 substituents, the substituents being independently from each other selected from the group consisting of hydrogen, CN, CO 2 H, CO 2 R 9 , halogen, NO 2 , OH, SH;C 1-12 alkyl, the C 1-12 -alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, NO 2 , CN, halogen, C 1 -C 8 alkoxy, NR 9 R 10 or C 6-12 aryl, this C 6-12 aryl residue being unsubstitued or substituted by C 1-8 alkyl, OH, NO 2 , CN, halogen, C 6-12 aryl, C 1 -C 8 alkoxy or NR 9 R 10 ;C 1-8 alkynyl, the C 1-8 alkynyl being unsubstituted or substituted by C 1-8 alkyl, OH, C 6-12 aryl or NR 9 R 10 ;C 6 -C 12 aryl, the C 6-12 aryl being unsubstituted or substituted by C 1-8 alkyl, OH, NO 2 , CN, halogen, C 6-12 aryl, C 1 -C 8 alkoxy, NR 9 R 10 or NR 11 R 12 ;C 6-12 -aryl-C 1-12 -alkyl, the C 6-12 -aryl-C 1-12 -alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, NO 2 , CN, halogen, C 6-12 aryl, C 1 -C 8 alkoxy or NR 9 R 10 ;OC 1-8 alkyl, the OC 1-8 alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, C 6-12 aryl or NR 11 R 12 ;NR 11 R 12 ;and SC 1-8 alkyl, the SC 1-8 alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, C 6-12 aryl or NR 9 R 10 ;E together with the two C atoms, to which the Y is double bonded and the squaric acid moiety is single bonded in formula (III), is a five or six membered aromatic or heteroaromatic cycle, the aromatic or heteroaromatic cycle can be annealed with a five or six membered aromatic or heteroaromatic cycle, the heteroaromatic cycles contain independently from each other 1, 2 or 3 heteroatoms selected from the group consisting of O, N and S, the aromatic or heteroaromatic cycles can independently from each other be further substituted by 1 to 6 substituents, the substituents being independently from each other selected from the group consisting of hydrogen, CN, halogen, NO 2 , OH, SH, C 1-8 alkyl, the C 1-8 alkyl being unsubstituted or substituted by C 1-8 alkyl, halogen, OH, C 6-12 aryl or NR 30 R 31 ;C 6 -C 12 aryl, the C 6-12 aryl being unsubstituted or substituted by C 1-8 alkyl, OH, NO 2 , CN, halogen, C 6-12 aryl, C 1 -C 8 alkoxy or NR 30 R 31 ;C 6-12 -aryl-C 1-12 -alkyl, the C 6-12 -aryl-C 1-12 -alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, NO 2 , CN, halogen, C 6-12 aryl, C 1 -C 8 alkoxy or NR 30 R 31 ;OC 1-8 alkyl, the OC 1-8 alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, C 6-12 aryl or NR 32 R 33 NR 32 R 33 ;and SC 1-8 alkyl, the SC 1-8 alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, C 6-12 aryl or-NR 30 R 31 ;R 9 , R 10 , R 11 , R 12 , R 30 , R 31 , R 32 and R 33 are independently from each other selected from the group consisting of hydrogen, C 1-8 alkyl and C 6-12 aryl;or R 11 together with R 12 , or, independently from R 11 and R 12 , R 32 together with R 33 form together with the N, to which they are connected, a five- or six-membered ring, which may contain further 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S;X is selected from the group consisting of O, S and imino-nitrogen N-R 1 ;Y is selected from the group consisting of O, S and imino-nitrogen N-R 2 ;R 1 and R 2 are independently from each other selected from the group consisting of hydrogen, C 1-12 alkyl, benzyl and C 6-12 aryl;the C 1-12 alkyl being unsubstituted or substituted by OH, C 6-12 aryl, halogen or NR 30 R 31 ;(2*) in formula (II) denotes the bond of the O atom of the group G1 to the divalent metal atom in formula (I);(3*) in formula (III) denotes the bond of the X residue of the group G1 to the divalent metal atom in formula (I).
- 6A process for the preparation of a compound of formula (I), as defined in any one of claims 1 to 5, by complexing reaction of one equivalent of a compound of formula (Ia) and one equivalent of a compound of formula (IIa) or (IIIa) with one equivalent of a divalent metal salt, wherein R 80 , R 81 , R 82 and R 83 are independently from each other C 1-8 alkyl or C 3-8 cycloalkyl;or R 80 and R 81 together with the C atom to which they are connected according to formula (I), or, independently from R 80 and R 81 , R 82 and R 83 together with the C atom to which they are connected according to formula (II), form a five or six membered aromatic or heteroaromatic cycle, the heteroaromatic cycle containing 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S;the aromatic or heteroaromatic cycle or the C 3-8 cycloalkyl can be annealed with a five or six membered aromatic or heteroaromatic cycle, this second heteroaromatic cycle containing 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S;the C 1-8 alkyl chains, the C 3-8 cycloalkyl, the aromatic or the heteroaromatic cycles can be substituted by 1 to 8 substituents, the substituents being independently from each other selected from the group consisting of hydrogen, CN, CO 2 H, CO 2 R 9 , halogen, NO 2 , OH, SH;C 1-12 alkyl, the C 1-12 -alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, NO 2 , CN, halogen, C 1 -C 8 alkoxy, NR 9 R 10 or C 6-12 aryl, this C 6-12 aryl residue being unsubstitued or substituted by C 1-8 alkyl, OH, NO 2 , CN, halogen, C 6-12 aryl, C 1 -C 8 alkoxy or NR 9 R 10 ;C 1-8 alkynyl, the C 1-8 alkynyl being unsubstituted or substituted by C 1-8 alkyl, OH, C 6-12 aryl or NR 9 R 10 ;C 6 -C 12 aryl, the C 6-12 aryl being unsubstituted or substituted by C 1-8 alkyl, OH, NO 2 , CN, halogen, C 6-12 aryl, C 1 -C 8 alkoxy, NR 9 R 10 or NR 11 R 12 ;C 6-12 -aryl-C 1-12 -alkyl, the C 6-12 -aryl-C 1-12 -alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, NO 2 , CN, halogen, C 6-12 aryl, C 1 -C 8 alkoxy or NR 9 R 10 ;OC 1-8 alkyl, the OC 1-8 alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, C 6-12 aryl or NR 11 R 12 ;NR 11 R 12 ;and SC 1-8 alkyl, the SC 1-8 alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, C 6-12 aryl or NR 9 R 10 ;E together with the two C atoms, to which the Y is double bonded and the squaric acid moiety is single bonded in formula (III), is a five or six membered aromatic or heteroaromatic cycle, the aromatic or heteroaromatic cycle can be annealed with a five or six membered aromatic or heteroaromatic cycle, the heteroaromatic cycles contain independently from each other 1, 2 or 3 heteroatoms selected from the group consisting of O, N and S, the aromatic or heteroaromatic cycles can independently from each other be further substituted by 1 to 6 substituents, the substituents being independently from each other selected from the group consisting of hydrogen, CN, halogen, NO 2 , OH, SH, C 1-8 alkyl, the C 1-8 alkyl being unsubstituted or substituted by C 1-8 alkyl, halogen, OH, C 6-12 aryl or NR 30 R 31 ;C 6 -C 12 aryl, the C 6-12 aryl being unsubstituted or substituted by C 1-8 alkyl, OH, NO 2 , CN, halogen, C 6-12 aryl, C 1 -C 8 alkoxy or NR 30 R 31 ;C 6-12 -aryl-C 1-12 -alkyl, the C 6-12 -aryl-C 1-12 -alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, NO 2 , CN, halogen, C 6-12 aryl, C 1 -C 8 alkoxy or NR 30 R 31 ;OC 1-8 alkyl, the OC 1-8 alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, C 6-12 aryl or NR 32 R 33 ;NR 32 R 33 ;and SC 1-8 alkyl, the SC 1-8 alkyl being unsubstituted or substituted by C 1-8 alkyl, OH, C 6-12 aryl or-NR 30 R 31 ;R 9 R 10 , R 11 , R 12 , R 30 , R 31 , R 32 and R 33 are independently from each other selected from the group consisting of hydrogen, C 1-8 alkyl and C 6-12 aryl;or R 11 together with R 12 , or, independently from R 11 and R 12 , R 32 together with R 33 form together with the N, to which they are connected, a five- or six-membered ring, which may contain further 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S;X is selected from the group consisting of O, S and imino-nitrogen N-R 1 ;Y is selected from the group consisting of O, S and imino-nitrogen N-R 2 ;R 1 and R 2 are independently from each other selected from the group consisting of hydrogen, C 1-12 alkyl, benzyl and C 6-12 aryl;the C 1-12 alkyl being unsubstituted or substituted by OH, C 6-12 aryl, halogen or NR 30 R 31 .
- 10A compound of formula (105), (106), (109), (110) or (112).
Independent claims5
109 paragraphs, as filed
0001The present invention relates to Nitro Schiff base metal complex dyes and their use in optical layers for optical data recording, preferably for optical data recording using a laser with a wavelength up to 450 nm.
0002The invention further relates to a write once read many (WORM) type optical data recording medium capable of recording and reproducing information with radiation of blue laser, which employs Nitro Schiff base metal complex dyes in the optical layer.
0003Recently, organic dyes have attracted considerable attentions in the field of diode-laser optical data storage. WORM type optical data recording media like commercial recordable compact discs (CD-R) and recordable digital versatile discs (DVD-R) can contain in the recording layer dyes based on phthalocyanine, hemicyanine, cyanine and metallized azo structures. These dyes are suitable in their respective fields with the laser wavelength criteria. Other general requirements for dye media are strong absorption, high reflectance, high recording sensitivity, enhancement of photosensitivity, low thermal conductivity as well as light and thermal stabilities, durability for storage or non-toxicity. Important criteria are also good read-out stability, which means high number of cycles at a given intensity of laser-light, and sufficient solubilities of the dyes in the organic solvents generally applied in the spin coating process.
0004At the recorded region of such an organic dye type optical data recording medium, the optical properties have been changed not only by a change in the optical characteristics and a decrease in the layer thickness resulting from the thermal decomposition of the dye, but also by a deformation of the substrate.
0005This recording principle is the same for CD-R and DVD-R, the difference remaining the spot size and the wavelength of the laser light used. CD-R are writable at a wavelength of from 770 to 830 nm and DVD-R, by using more recent compact high-performance red diode lasers, at a wavelength from 600 to 700 nm achieving then a 6- to 8 fold improvement in data packing density in comparison with conventional CDs.
0006However, considering factors such as the recent spread of electronic networks (e.g. Internet) and the emergence of high definition television (HDTV) broadcasting, inexpensive and convenient recording media, capable of recording image information at even larger capacity, are required. While DVD-R's sufficiently serve as high-capacity recording media at present, demand for larger capacity and higher density has increased.
0007Blu-ray<sup>®</sup> discs (Blu-ray<sup>®</sup> disc is a standard developed by Hitachi Ltd., LG Electronics Inc., Matsushita Electric Industrial Co. Ltd., Pioneer Corporation, Royal Philips Electronics, Samsung Electronics Co. Ltd., Sharp Corporation, Sony Corporation, Thomson Multimedia) or HD-DVD discs (a standard developed by Toshiba and NEC) are going to be the next milestone in optical data recording technology. By these new specifications the data storage may be increased up to 27 Gigabytes per recording layer for a 12 cm diameter disc. By adopting a blue diode laser with a wavelength of 405 nm (GaN or SHG laser diodes), the pit size and track interval can be further reduced, again increasing the storage capacity by an order of magnitude.
0008The construction of such optical data recording media is known in the art. The optical recording medium comprises preferably a substrate with a guide groove for laser beam tracking, a recording layer, also called optical layer, containing an organic dye as the main component, a reflective layer and a protective layer. When recording/readout is carried out through the substrate, a transparent substrate is employed. As such a transparent substrate, one made of a resin such as polycarbonate, polymethacrylate or amorphous polyolefin, one made of glass or one having a resin layer made of radiation curable resin, i.e. photopolymerizable resin, formed on glass, may, for example, be employed. Advanced optical data recording media may comprise further layers, such as protective layers, adhesive layers or even additional optical recording layers.
0009For blue diode-laser optical data storage a variety of dye compounds has been proposed in the literature.
0010Monosubstituted squaric acid metal complex dyes, for example the compound of formula (101), are known from <patcit id="pcit0001" dnum="WO2006053834A"><text>WO 2006/053834 A</text></patcit>. <chemistry id="chem0001" num="0001"><img file="EP1925643A1_D0001.tif" /></chemistry>
0011Schiff base based metal complexed dyes are known from <patcit id="pcit0002" dnum="JP200434645B"><text>JP 200434645</text></patcit>.
0012Unfortunately the dye compounds described so far still show disadvantages which impede their satisfactory use as dyes for optical data storage.
0013There is a still a need for an optical data recording medium that is capable of recording data at high density with improved recording characteristics and with improved read-out stabilities.
0014Surprisingly the object was achieved by using compounds comprising Nitro Schiff base metal complex dyes.
0015In the following text "halogen" represents F, Cl, Br or I, preferably F, Cl or Br, more preferably F or Cl, even more preferably Cl, if not otherwise stated; "alkyl" represents linear and branched alkyl; "alkylthio" represents linear and branched alkylthio; and "alkoxy" represents linear and branched alkoxy; any alkyl, alkylthio and cycloalkyl group being unsubstituted, partially or completely substituted by one or more halogen atoms (preferably halogenated alkyl are selected from the group consisting of CF<sub>3</sub>, CF<sub>2</sub>CF<sub>3</sub>, CF<sub>2</sub>CF<sub>2</sub>CF<sub>3</sub> and chloromethyl, more preferably from CF<sub>3</sub>, CF<sub>2</sub>CF<sub>3</sub> and CF<sub>2</sub>CF<sub>2</sub>CF<sub>3</sub>); if not otherwise stated.
0016Subject of the invention is a compound of formula (I), <chemistry id="chem0002" num="0002"><img file="EP1925643A1_D0002.tif" /></chemistry> wherein <dl id="dl0001" compact="compact"><dt>M</dt><dd>is a divalent metal atom or oxidized divalent metal atom, preferably selected from main groups 1 to 5 or from transition groups 1 or 2 or 4 to 8 of the Periodic Table of the Chemical Elements;</dd><dt>G1</dt><dd>is a group of formula (II) or of formula (III); <chemistry id="chem0003" num="0003"><img file="EP1925643A1_D0003.tif" /></chemistry></dd><dt>R<sup>80</sup>, R<sup>81</sup>, R<sup>82</sup> and R<sup>83</sup></dt><dd>are independently from each other C<sub>1-8</sub> alkyl or C<sub>3-8</sub> cycloalkyl; or</dd><dt>R<sup>80</sup> and R<sup>81</sup></dt><dd>together with the C atom to which they are connected according to formula (I), or, independently from R<sup>80</sup> and R<sup>81</sup>, R<sup>82</sup> and R<sup>83</sup> together with the C atom to which they are connected according to formula (II), form a five or six membered aromatic or heteroaromatic cycle, the heteroaromatic cycle containing 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S; the aromatic or heteroaromatic cycle or the C<sub>3-8</sub> cycloalkyl can be annealed with a five or six membered aromatic or heteroaromatic cycle, this second heteroaromatic cycle containing 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S; the C<sub>1-8</sub> alkyl chains, the C<sub>3-8</sub> cycloalkyl, the aromatic or the heteroaromatic cycles can be substituted by 1 to 8 substituents, the substituents being independently from each other selected from the group consisting of hydrogen, CN, CO<sub>2</sub>H, CO<sub>2</sub>R<sup>9</sup>, halogen, NO<sub>2</sub>, OH, SH; C<sub>1-12</sub> alkyl, the C<sub>1-12</sub>-alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>1</sub>-C<sub>8</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or C<sub>6-12</sub> aryl, this C<sub>6-12</sub> aryl residue being unsubstitued or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; C<sub>1-8</sub> alkynyl, the C<sub>1-8</sub> alkynyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>9</sup>R<sup>10</sup>, C<sub>6</sub>-C<sub>12</sub> aryl, the C<sub>6-12</sub> aryl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or NR<sup>11</sup>R<sup>12</sup>; C<sub>6-12</sub>-aryl-C<sub>1-12</sub>-alkyl, the C<sub>6-12</sub>-aryl-C<sub>1-12</sub>-alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; OC<sub>1-8</sub> alkyl, the OC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>11</sup>R<sup>12</sup>; NR<sup>11</sup>R<sup>12</sup> ; and SC<sub>1-8</sub> alkyl, the SC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>9</sup>R<sup>10</sup>;</dd><dt>E</dt><dd>together with the two C atoms, to which the Y is double bonded and the squaric acid moiety is single bonded in formula (III), is a five or six membered aromatic or heteroaromatic cycle, the aromatic or heteroaromatic cycle can be annealed with a five or six membered aromatic or heteroaromatic cycle, the heteroaromatic cycles contain independently from each other 1, 2 or 3 heteroatoms selected from the group consisting of O, N and S, the aromatic or heteroaromatic cycles can independently from each other be further substituted by 1 to 6 substituents, the substituents being independently from each other selected from the group consisting of hydrogen, CN, halogen, NO<sub>2</sub>, OH, SH, C<sub>1-8</sub> alkyl, the C<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, halogen, OH, C<sub>6-12</sub> aryl or NR<sup>30</sup>R<sup>31</sup>; C<sub>6</sub>-C<sub>12</sub> aryl, the C<sub>6-12</sub> aryl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>30</sup>R<sup>31</sup>; C<sub>6-12</sub>-aryl-C<sub>1-12</sub>-alkyl, the C<sub>6-12</sub>-aryl-C<sub>1-12</sub>-alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>30</sup>R<sup>31</sup>; OC<sub>1-8</sub> alkyl, the OC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>32</sup>R<sup>33</sup>; NR<sup>32</sup>R<sup>33</sup>; and SC<sub>1-8</sub> alkyl, the SC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or-NR<sup>30</sup>R<sup>31</sup>;</dd><dt>R<sup>9</sup>, R<sup>10</sup>, R<sup>11</sup>, R<sup>12</sup>, R<sup>30</sup>, R<sup>31</sup>, R<sup>32</sup> and R<sup>33</sup></dt><dd>are independently from each other selected from the group consisting of hydrogen, C<sub>1-8</sub> alkyl and C<sub>6-12</sub> aryl; or</dd><dt>R<sup>11</sup> together with R<sup>12</sup>,</dt><dd>or, independently from R<sup>11</sup> and R<sup>12</sup>, R<sup>32</sup> together with R<sup>33</sup> form together with the N, to which they are connected, a five- or six-membered ring, which may contain further 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S;</dd><dt>X</dt><dd>is selected from the group consisting of O, S and imino-nitrogen N-R<sup>1</sup>;</dd><dt>Y</dt><dd>is selected from the group consisting of O, S and imino-nitrogen N-R<sup>2</sup>;</dd><dt>R<sup>1</sup> and R<sup>2</sup></dt><dd>are independently from each other selected from the group consisting of hydrogen, C<sub>1-12</sub> alkyl, benzyl and C<sub>6-12</sub> aryl; the C<sub>1-12</sub> alkyl being unsubstituted or substituted by OH, C<sub>6-12</sub> aryl, halogen or NR<sup>30</sup>R<sup>31</sup>;</dd><dt>(2*)</dt><dd>in formula (II) denotes the bond of the O atom of the group G1 to the divalent metal atom in formula (I);</dd><dt>(3*)</dt><dd>in formula (III) denotes the bond of the X residue of the group G1 to the divalent metal atom in formula (I).</dd></dl>
0017In a preferred aspect, subject of the invention is a compound of formula (I), wherein <dl id="dl0002" compact="compact"><dt>M</dt><dd>represents a divalent metal atom or oxidized divalent metal atom selected from the group consisting of Ca, Sr, Ba, Al, Ga, In, Sc, Y, Ti, Zr, V(O), Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;</dd><dt>R<sup>80</sup> and R<sup>81</sup></dt><dd>together with the C atom to which they are connected according to formula (I), and, independently from R<sup>80</sup> and R<sup>81</sup>, R<sup>82</sup> and R<sup>83</sup> together with the C atom to which they are connected according to formula (II), represent a residue selected from the group of residues consisting of formulae (f), (g), (h), (i), (j), (k), (l), (m), (n) and (o), preferably of formulae (f), (g), (h), (j), (l) and (n), and their tautomeric forms, <chemistry id="chem0004" num="0004"><img file="EP1925643A1_D0004.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP1925643A1_D0005.tif" /></chemistry><chemistry id="chem0006" num="0006"><img file="EP1925643A1_D0006.tif" /></chemistry><chemistry id="chem0007" num="0007"><img file="EP1925643A1_D0007.tif" /></chemistry> wherein</dd><dt>(4*)</dt><dd>denotes the bond between the C atom, to which R<sup>80</sup> and R<sup>81</sup> in formula (I) or R<sup>82</sup> and R<sup>83</sup> in formula (II) are connected, and the N atom in formula (I) or (II),</dd><dt>n</dt><dd>represents a number from 0 to 5;</dd><dt>R<sup>40</sup> and R<sup>41</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, C<sub>1-12</sub> alkyl, the C<sub>1-12</sub>-alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>1</sub>-C<sub>8</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or C<sub>6-12</sub> aryl, this C<sub>6-12</sub> aryl residue being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; C<sub>6-8</sub>-aryl-C<sub>1-8</sub>-alkyl, the C<sub>6-8</sub>-aryl-C<sub>1-8</sub>-alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-8</sub> aryl, C<sub>1</sub>-C<sub>6</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; and C<sub>6</sub>-C<sub>12</sub> aryl, the C<sub>6-12</sub> aryl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>;</dd><dt>R<sup>42</sup> to R<sup>46</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, CN, CO<sub>2</sub>H, CO<sub>2</sub>R<sup>9</sup>, halogen, NO<sub>2</sub>, OH, SH; OC<sub>1-8</sub> alkyl, the OC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>11</sup>R<sup>12</sup>; NR<sup>11</sup>R<sup>12</sup>; C<sub>1-8</sub> alkyl, the C<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, halogen, OH, C<sub>6-12</sub> aryl or NR<sup>9</sup>R<sup>10</sup>; C<sub>1-8</sub> alkynyl, the C<sub>1-8</sub>-alkynyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>11</sup>R<sup>12</sup>; SC<sub>1-8</sub> alkyl, the SC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>9</sup>R<sup>10</sup>; and C<sub>6-12</sub> aryl, the C<sub>6-12</sub> aryl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or NR<sup>11</sup>R<sup>12</sup>;</dd><dt>E</dt><dd>together with the two C atoms, to which the Y is double bonded and the squaric acid moiety is single bonded in formula (III), and together with the Y in formula (III), is selected from the group consisting of residues of formulae (g2), (h2), (i2), (j2), (k2), (l2), (m2), (n2), (o2), (p2), (q2), (r2) and (s2), preferably of formulae (j2), (k2), (l2) and (m2), even more preferably of formulae (m2), and their tautomeric forms, <chemistry id="chem0008" num="0008"><img file="EP1925643A1_D0008.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP1925643A1_D0009.tif" /></chemistry><chemistry id="chem0010" num="0010"><img file="EP1925643A1_D0010.tif" /></chemistry><chemistry id="chem0011" num="0011"><img file="EP1925643A1_D0011.tif" /></chemistry><chemistry id="chem0012" num="0012"><img file="EP1925643A1_D0012.tif" /></chemistry> wherein</dd><dt>(5*)</dt><dd>denotes the bond between E and the squaric acid moiety in formula (III);</dd><dt>R<sup>60</sup> and R<sup>61</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, C<sub>1-8</sub> alkyl, the C<sub>1-8</sub>-alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, halogen, OH, C<sub>6-12</sub> aryl or NR<sup>30</sup>R<sup>31</sup>; C<sub>6-12</sub>-aryl-C<sub>1-12</sub>-alkyl, the C<sub>6-12</sub>-aryl-C<sub>1-12</sub>-alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>30</sup>R<sup>31</sup>; and C<sub>6</sub>-C<sub>12</sub> aryl, the C<sub>6-12</sub> aryl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>30</sup>R<sup>31</sup>;</dd><dt>R<sup>62</sup> to R<sup>65</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, CN, halogen, NO<sub>2</sub>, OH, OC<sub>1-8</sub> alkyl, the OC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>32</sup>R<sup>31</sup>; NR<sup>32</sup>R<sup>33</sup>; C<sub>1-8</sub> alkyl, the C<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, halogen, OH, C<sub>6-12</sub> aryl or NR<sup>30</sup>R<sup>31</sup>; SC<sub>1-8</sub> alkyl, the SC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR <sup>30</sup>R <sup>31</sup>; and C<sub>6-12</sub> aryl, the C<sub>6-12</sub> aryl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>30</sup>R<sup>31</sup>;</dd><dt>R<sup>9</sup>,R<sup>10</sup>, R<sup>11</sup>, R<sup>12</sup>, R<sup>30</sup>, R<sup>31</sup>, R<sup>32</sup> and R<sup>33</sup></dt><dd>are independently from each other selected from the group consisting of hydrogen, C<sub>1-8</sub> alkyl and C<sub>6-12</sub> aryl; or</dd><dt>R<sup>11</sup> together with R<sup>12</sup>,</dt><dd>or, independently from R<sup>11</sup> and R<sup>12</sup>, R<sup>32</sup> together with R<sup>33</sup> form together with the N, to which they are connected, a five- or six-membered ring, which may contain further 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S;</dd><dt>X</dt><dd>represents O or S.</dd></dl>
0018In a more preferred aspect, subject of the invention is a compound of formula (I), <dl id="dl0003" compact="compact"><dt>M</dt><dd>represents a divalent metal atom or oxidized divalent metal atom selected from the group consisting of Al, Y, Zr, V(O), Cr, Mn, Fe, Co, Ni, Cu, Zn and Yb;</dd></dl> R<sup>80</sup> and R<sup>81</sup> together with the C atom to which they are connected according to formula (I), represent a residue selected from the group of residues consisting of formulae (f), (g), (h), (j), (l) and (n) and their tautomeric forms, <dl id="dl0004" compact="compact"><dt>n</dt><dd>represents a number from 0 to 5;</dd><dt>R<sup>40</sup>and R<sup>41</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, C<sub>1-6</sub> alkyl, the C<sub>1-6</sub>-alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, halogen, OH, NO<sub>2</sub>, CN, C<sub>1</sub>-C<sub>6</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or C<sub>6-8</sub> aryl, this C<sub>6-8</sub> aryl residue being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-8</sub> aryl, C<sub>1</sub>-C<sub>6</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; C<sub>6-8</sub>-aryl-C<sub>1-8</sub>-alkyl, the C<sub>6-8</sub>-aryl-C<sub>1-8</sub>-alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-8</sub> aryl, C<sub>1</sub>-C<sub>6</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; and C<sub>6</sub>-C<sub>8</sub> aryl, the C<sub>6-8</sub> aryl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-8</sub> aryl, C<sub>1</sub>-C<sub>6</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>;</dd><dt>R<sup>42</sup> to R<sup>46</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, CN, CO<sub>2</sub>H, CO<sub>2</sub>R<sup>9</sup>, halogen, NO<sub>2</sub>, OH, SH; OC<sub>1-6</sub> alkyl, the OC<sub>1-6</sub> alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, C<sub>6-8</sub> aryl or NR<sup>11</sup>R<sup>12</sup>; NR<sup>11</sup>R<sup>12</sup>; C<sub>1-6</sub> alkyl, the C<sub>1-6</sub> alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, halogen, OH, C<sub>6-8</sub> aryl or NR<sup>9</sup>R<sup>10</sup>; C<sub>1-6</sub> alkynyl, the C<sub>1-6</sub>-alkynyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, C<sub>6-8</sub> aryl or NR<sup>11</sup> R<sup>12</sup>, preferably unsubstituted ethynyl; SC<sub>1-6</sub> alkyl, the SC<sub>1-6</sub> alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, C<sub>6-8</sub> aryl or NR<sup>9</sup>R<sup>10</sup>; and C<sub>6-8</sub> aryl, the C<sub>6-8</sub> aryl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-8</sub> aryl, C<sub>1</sub>-C<sub>6</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or NR<sup>11</sup>R<sup>12</sup>;</dd><dt>G1</dt><dd>is a group of formula (III);</dd><dt>E</dt><dd>together with the two C atoms, to which the Y is double bonded and the squaric acid moiety is single bonded in formula (III), and together with the Y in formula (III), is selected from the group consisting of residues of formulae (j2), (k2), (l2) and (m2) and their tautomeric forms,</dd><dt>R<sup>60</sup> and R<sup>61</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen; C<sub>1-8</sub> alkyl, the C<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>30</sup>R<sup>31</sup>; C<sub>6-12</sub>-aryl-C<sub>1-12</sub>-alkyl, the C<sub>6-12</sub>-aryl-C<sub>1-12</sub>-alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>30</sup>R<sup>31</sup>; and C<sub>6-12</sub> aryl, the C<sub>6-12</sub> aryl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>30</sup>R<sup>31</sup>;</dd><dt>R<sup>62</sup> to R<sup>65</sup></dt><dd>independently from each other selected from the group consisting of hydrogen, CN, halogen, NO<sub>2</sub>, OH; OC<sub>1-8</sub> alkyl, the OC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>30</sup>R<sup>31</sup>; NR<sup>32</sup>R<sup>33</sup>; C<sub>1-8</sub> alkyl, the C<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, halogen, OH, C<sub>6-12</sub> aryl or NR<sup>30</sup>R<sup>31</sup>; SC<sub>1-8</sub> alkyl, the SC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>30</sup>R<sup>31</sup>; and C<sub>6-12</sub> aryl, the C<sub>6-12</sub> aryl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>30</sup>R<sup>31</sup>;</dd><dt>R<sup>9</sup>,R<sup>10</sup>, R<sup>11</sup>, R<sup>12</sup>, R<sup>30</sup>, R<sup>31</sup>, R<sup>32</sup> and R<sup>33</sup></dt><dd>are independently from each other selected from the group consisting of hydrogen, C<sub>1-8</sub> alkyl and C<sub>6-12</sub> aryl, preferably of hydrogen, methyl and ethyl; or</dd><dt>R<sup>11</sup> together with R<sup>12</sup>,</dt><dd>or, independently from R<sup>11</sup> and R<sup>12</sup>, R<sup>32</sup> together with R<sup>33</sup> form together with the N, to which they are connected, a five- or six-membered ring, which may contain further 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S, preferably a morpholino ring;</dd><dt>X</dt><dd>represents O.</dd></dl>
0019In another more preferred aspect, subject of the invention is a compound of formula (I), <dl id="dl0005" compact="compact"><dt>M</dt><dd>represents a divalent metal atom or oxidized divalent metal atom selected from the group consisting of Al, Y, Zr, V(O), Cr, Mn, Fe, Co, Ni, Cu, Zn and Yb;</dd><dt>G1</dt><dd>is a group of formula (II);</dd></dl> R<sup>80</sup> and R<sup>81</sup> together with the C atom to which they are connected according to formula (I), and R<sup>82</sup> and R<sup>83</sup> together with the C atom to which they are connected according to formula (II), are identical, i.e. the compound of formula (I) represents a homoleptic complex, and represent a residue selected from the group of residues consisting of formulae (f), (g), (h), (j), (l) and (n) and their tautomeric forms, <dl id="dl0006" compact="compact"><dt>n</dt><dd>represents a number from 0 to 5;</dd><dt>R<sup>40</sup> and R<sup>41</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, C<sub>1-6</sub> alkyl, the C<sub>1-6</sub>-alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>1</sub>-C<sub>6</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or C<sub>6-8</sub> aryl, this C<sub>6-8</sub> aryl residue being unsubstitued or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-8</sub> aryl, C<sub>1</sub>-C<sub>6</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; C<sub>6-8</sub>-aryl-C<sub>1-8</sub>-alkyl, the C<sub>6-8</sub>-aryl-C<sub>1-8</sub>-alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-8</sub> aryl, C<sub>1</sub>-C<sub>6</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; and C<sub>6</sub>-C<sub>8</sub> aryl, the C<sub>6-8</sub> aryl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-8</sub> aryl, C<sub>1</sub>-C<sub>6</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>;</dd><dt>R<sup>42</sup> to R<sup>46</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, CN, CO<sub>2</sub>H, CO<sub>2</sub>R<sup>9</sup>, halogen, NO<sub>2</sub>, OH, SH; OC<sub>1-6</sub> alkyl, the OC<sub>1-6</sub> alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, C<sub>6-8</sub> aryl or NR<sup>11</sup>R<sup>12</sup>; NR<sup>11</sup>R<sup>12</sup>, C<sub>1-6</sub> alkyl, the C<sub>1-6</sub> alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, halogen, OH, C<sub>6-8</sub> aryl or NR<sup>9</sup>R<sup>10</sup>; C<sub>1-6</sub> alkynyl, the C<sub>1-6</sub>-alkynyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, C<sub>6-8</sub> aryl or NR<sup>11</sup>R<sup>12</sup>, preferably unsubstituted ethynyl; SC<sub>1-6</sub> alkyl, the SC<sub>1-6</sub> alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, C<sub>6-8</sub> aryl or NR<sup>9</sup>R<sup>10</sup>; and C<sub>6-8</sub> aryl, the C<sub>6-8</sub> aryl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-8</sub> aryl, C<sub>1</sub>-C<sub>6</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or NR<sup>11</sup>R<sup>12</sup>;</dd><dt>R<sup>9</sup>, R<sup>10</sup>, R<sup>11</sup> and R<sup>12</sup></dt><dd>are independently from each other selected from the group consisting of hydrogen, C<sub>1-8</sub> alkyl and C<sub>6-12</sub> aryl, preferably of hydrogen, methyl and ethyl; or</dd><dt>R<sup>11</sup> together with R<sup>12</sup></dt><dd>form together with the N, to which they are connected, a five- or six-membered ring, which may contain further 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S, preferably a morpholino ring.</dd></dl>
0020In another more preferred aspect, subject of the invention is a compound of formula (I), <dl id="dl0007" compact="compact"><dt>M</dt><dd>represents a divalent metal atom or oxidized divalent metal atom selected from the group consisting of Al, Y, Zr, V(O), Cr, Mn, Fe, Co, Ni, Cu, Zn and Yb;</dd><dt>G1</dt><dd>is a group of formula (II);</dd></dl> R<sup>80</sup> and R<sup>81</sup> together with the C atom to which they are connected according to formula (I), and, independently from R<sup>80</sup> and R<sup>81</sup>, R<sup>82</sup> and R<sup>83</sup> together with the C atom to which they are connected according to formula (II), are different, i.e. the compound of formula (I) represents a heteroleptic complex, and represent a residue selected from the group of residues consisting of formulae (f), (g), (h), (j), (l) and (n) and their tautomeric forms, <dl id="dl0008" compact="compact"><dt>n</dt><dd>represents a number from 0 to 5;</dd><dt>R<sup>40</sup>and R<sup>41</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, C<sub>1-6</sub> alkyl, the C<sub>1-6</sub>-alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>1</sub>-C<sub>6</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or C<sub>6-8</sub> aryl, this C<sub>6-8</sub> aryl residue being unsubstitued or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-8</sub> aryl, C<sub>1</sub>-C<sub>6</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; C<sub>6-8</sub>-aryl-C<sub>1-8</sub>-alkyl, the C<sub>6-8</sub>aryl-C<sub>1-8</sub>-alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-8</sub> aryl, C<sub>1</sub>-C<sub>6</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; and C<sub>6</sub>-C<sub>8</sub> aryl, the C<sub>6-8</sub> aryl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-8</sub> aryl, C<sub>1</sub>-C<sub>6</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>;</dd><dt>R<sup>42</sup> to R<sup>46</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, CN, CO<sub>2</sub>H, CO<sub>2</sub>R<sup>9</sup>, halogen, NO<sub>2</sub>, OH, SH; OC<sub>1-6</sub> alkyl, the OC<sub>1-6</sub> alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, C<sub>6-8</sub> aryl or NR<sup>11</sup>R<sup>12</sup>; NR<sup>11</sup>R<sup>12</sup>; C<sub>1-6</sub> alkyl, the C<sub>1-6</sub> alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, halogen, OH, C<sub>6-8</sub> aryl or NR<sup>9</sup>R<sup>10</sup>; C<sub>1-6</sub> alkynyl, the C<sub>1-6</sub>-alkynyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, C<sub>6-8</sub> aryl or NR<sup>11</sup>R<sup>12</sup>, preferably unsubstituted ethynyl; SC<sub>1-6</sub> alkyl, the SC<sub>1-6</sub> alkyl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, C<sub>6-8</sub> aryl or NR<sup>9</sup>R<sup>10</sup>; and C<sub>6-8</sub> aryl, the C<sub>6-8</sub> aryl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-8</sub> aryl, C<sub>1</sub>-C<sub>6</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or NR<sup>11</sup>R<sup>12</sup>;</dd><dt>R<sup>9</sup>, R<sup>10</sup>, R<sup>11</sup> and R<sup>12</sup></dt><dd>are independently from each other selected from the group consisting of hydrogen, C<sub>1-8</sub> alkyl and C<sub>6-12</sub> aryl, preferably of hydrogen, methyl and ethyl; or</dd><dt>R<sup>11</sup> together with R<sup>12</sup></dt><dd>form together with the N, to which they are connected, a five- or six-membered ring, which may contain further 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S, preferably a morpholino ring.</dd></dl>
0021In an even more preferred aspect, subject of the invention is a compound of formula (I), <dl id="dl0009" compact="compact"><dt>M</dt><dd>in formula (I) is a divalent metal atom or oxidized divalent metal atom selected from the group consisting of V(O), Cr, Mn, Co, Fe, Ni, Cu and Zn;</dd><dt>R<sup>80</sup> and R<sup>81</sup></dt><dd>together with the C atom to which they are connected according to formula (I), represent a residue selected from the group of residues consisting of formulae (f), (g), (h), (j), (l) and (n) and their tautomeric forms,</dd><dt>n</dt><dd>represents a number from 0 to 2;</dd><dt>R<sup>40</sup> and R<sup>41</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, C<sub>1-6</sub> alkyl, the C<sub>1-6</sub>-alkyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, F, Br, Cl, C<sub>1</sub>-C<sub>3</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or C<sub>6</sub>-aryl, this C<sub>6</sub>-aryl residue being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, F, Br, Cl, C<sub>6</sub> aryl, C<sub>1</sub>-C<sub>3</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; C<sub>6</sub>-aryl-C<sub>1-6</sub>-alkyl, the C<sub>6</sub>-aryl-C<sub>1-6</sub>-alkyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, NO<sub>2</sub>, CN, F, Br, Cl, C<sub>6</sub> aryl, C<sub>1</sub>-C<sub>3</sub> alkoxy, or NR<sup>9</sup>R<sup>10</sup>; and C<sub>6</sub>-aryl, the C<sub>6</sub>-aryl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, F, Br, Cl, C<sub>6</sub> aryl, C<sub>1</sub>-C<sub>3</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>;</dd><dt>R<sup>42</sup> to R<sup>46</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, CN, CO<sub>2</sub>H, CO<sub>2</sub>R<sup>9</sup>, halogen, NO<sub>2</sub>, OH, SH; OC<sub>1-3</sub> alkyl, the OC<sub>1-3</sub> alkyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, C<sub>6</sub> aryl or NR<sup>11</sup> R<sup>12</sup>; NR<sup>11</sup>R<sup>12</sup>; C<sub>1-3</sub> alkyl, the C<sub>1-3</sub> alkyl being unsubstituted or substituted by methyl, ethyl, propyl, F, Br, Cl, OH, C<sub>6</sub> aryl or NR<sup>9</sup>R<sup>10</sup>; C<sub>1-3</sub> alkynyl, the C<sub>1-3</sub>-alkynyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, C<sub>6-8</sub> aryl or NR<sup>11</sup>R<sup>12</sup>, preferably unsubstituted ethynyl; SC<sub>1-3</sub> alkyl, the SC<sub>1-3</sub> alkyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, C<sub>6</sub> aryl or NR<sup>9</sup>R<sup>10</sup>; and C<sub>6</sub> aryl, the C<sub>6</sub> aryl being unsubstituted or substituted by methyl, ethyl, propyl, OH, NO<sub>2</sub>, CN, F, Br, Cl, C<sub>6</sub> aryl, C<sub>1</sub>-C<sub>3</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or NR<sup>11</sup>R<sup>12</sup>;</dd><dt>G1</dt><dd>is a group of formula (III);</dd><dt>E</dt><dd>together with the two C atoms, to which the Y is double bonded and the squaric acid moiety is single bonded in formula (III), and together with the Y in formula (III), is residue of formula (m2);</dd><dt>R<sup>60</sup></dt><dd>represents phenyl or p-tolyl, preferably phenyl;</dd><dt>R<sup>61</sup></dt><dd>represents methyl or benzyl, preferably methyl;</dd><dt>R<sup>62</sup></dt><dd>represents methyl or phenyl, preferably methyl;</dd><dt>R<sup>9</sup>, R<sup>10</sup>, R<sup>11</sup> and R<sup>12</sup></dt><dd>are independently from each other selected from the group consisting of hydrogen, C<sub>1-8</sub> alkyl and C<sub>6-12</sub> aryl, preferably of hydrogen, methyl and ethyl; or</dd><dt>R<sup>11</sup> together with R<sup>12</sup></dt><dd>form together with the N, to which they are connected, a five- or six-membered ring, which may contain further 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S, preferably a morpholino ring.</dd></dl>
0022In another even more preferred aspect, subject of the invention is a compound of formula (I), <dl id="dl0010" compact="compact"><dt>M</dt><dd>represents a divalent metal atom or oxidized divalent metal atom selected from the group consisting of V(O), Cr, Mn, Co, Fe, Ni, Cu and Zn;</dd><dt>G1</dt><dd>is a group of formula (II);</dd><dt>R<sup>80</sup> and R<sup>81</sup></dt><dd>together with the C atom to which they are connected according to formula (I), and R<sup>82</sup> and R<sup>83</sup> together with the C atom to which they are connected according to formula (II), are identical, i.e. the compound of formula (I) represents a homoleptic complex, and represent a residue selected from the group of residues consisting of formulae (f), (g), (h), (j), (l) and (n) and their tautomeric forms,</dd><dt>n</dt><dd>represents a number from 0 to 2;</dd><dt>R<sup>40</sup> and R<sup>41</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, C<sub>1-6</sub> alkyl, the C<sub>1-6</sub>-alkyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, F, Br, Cl , C<sub>1</sub>-C<sub>3</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or C<sub>6</sub>-aryl, this C<sub>6</sub>-aryl residue being unsubstitued or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, F, Br, Cl, C<sub>6</sub> aryl, C<sub>1</sub>-C<sub>3</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; C<sub>6</sub>-aryl-C<sub>1-6</sub>-alkyl, the C<sub>6</sub>-aryl-C<sub>1-6</sub>-alkyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, NO<sub>2</sub>, CN, F, Br, Cl, C<sub>6</sub> aryl, C<sub>1</sub>-C<sub>3</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; and C<sub>6</sub>-aryl, the C<sub>6</sub>-aryl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, F, Br, Cl, C<sub>6</sub> aryl, C<sub>1</sub>-C<sub>3</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>;</dd><dt>R<sup>42</sup> to R<sup>46</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, CN, CO<sub>2</sub>H, CO<sub>2</sub>R<sup>9</sup>, halogen, NO<sub>2</sub>, OH, SH; OC<sub>1-3</sub> alkyl, the OC<sub>1-3</sub> alkyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, C<sub>6</sub> aryl or NR<sup>11</sup>R<sup>12</sup>; NR<sup>11</sup>R<sup>12</sup> ; C<sub>1-3</sub> alkyl, the C<sub>1-3</sub> alkyl being unsubstituted or substituted by methyl, ethyl, propyl, F, Br, Cl, OH, C<sub>6</sub> aryl or NR<sup>9</sup>R<sup>10</sup>; C<sub>1-3</sub> alkynyl, the C<sub>1-3</sub>-alkynyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, C<sub>6-8</sub> aryl or NR<sup>11</sup>R<sup>12</sup>, preferably unsubstituted ethynyl; SC<sub>1-3</sub> alkyl, the SC<sub>1-3</sub> alkyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, C<sub>6</sub> aryl or NR<sup>9</sup>R<sup>10</sup> ; and C<sub>6</sub> aryl, the C<sub>6</sub> aryl being unsubstituted or substituted by methyl, ethyl, propyl, OH, NO<sub>2</sub>, CN, F, Br, Cl, C<sub>6</sub> aryl, C<sub>1</sub>-C<sub>3</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or NR<sup>11</sup>R<sup>12</sup>;</dd><dt>R<sup>9</sup>, R<sup>10</sup>, R<sup>11</sup> and R<sup>12</sup></dt><dd>are independently from each other selected from the group consisting of hydrogen, C<sub>1-8</sub> alkyl and C<sub>6-12</sub> aryl, preferably of hydrogen, methyl and ethyl; or</dd><dt>R<sup>11</sup> together with R<sup>12</sup></dt><dd>form together with the N, to which they are connected, a five- or six-membered ring, which may contain further 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S, preferably a morpholino ring.</dd></dl>
0023In another even more preferred aspect, subject of the invention is a compound of formula (I), <dl id="dl0011" compact="compact"><dt>M</dt><dd>represents a divalent metal atom or oxidized divalent metal atom selected from the group consisting of Al, Y, Zr, V(O), Cr, Mn, Fe, Co, Ni, Cu, Zn and Yb;</dd><dt>G1</dt><dd>is a group of formula (II);</dd></dl> R<sup>80</sup> and R<sup>81</sup> together with the C atom to which they are connected according to formula (I), and, independently from R<sup>80</sup> and R<sup>81</sup>, R<sup>82</sup> and R<sup>83</sup> together with the C atom to which they are connected according to formula (II), are different, i.e. the compound of formula (I) represents a heteroleptic complex, and represent a residue selected from the group of residues consisting of formulae (f), (g), (h), (j), (l) and (n) and their tautomeric forms, <dl id="dl0012" compact="compact"><dt>n</dt><dd>represents a number from 0 to 2;</dd><dt>R<sup>40</sup> and R<sup>41</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, C<sub>1-6</sub> alkyl, the C<sub>1-6</sub>-alkyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, F, Br, Cl, C<sub>1</sub>-C<sub>3</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or C<sub>6</sub>-aryl, this C<sub>6</sub>-aryl residue being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, F, Br, Cl, C<sub>6</sub> aryl, C<sub>1</sub>-C<sub>3</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; C<sub>6</sub>-aryl-C<sub>1-6</sub>-alkyl, the C<sub>6</sub>-aryl-C<sub>1-6</sub>-alkyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, NO<sub>2</sub>, CN, F, Br, Cl, C<sub>6</sub> aryl, C<sub>1</sub>-C<sub>3</sub> alkoxy, or NR<sup>9</sup>R<sup>10</sup>; and C<sub>6</sub>-aryl, the C<sub>6</sub>-aryl being unsubstituted or substituted by C<sub>1-6</sub> alkyl, OH, NO<sub>2</sub>, CN, F, Br, Cl, C<sub>6</sub> aryl, C<sub>1</sub>-C<sub>3</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>;</dd><dt>R<sup>42</sup> to R<sup>46</sup></dt><dd>independently from each other are selected from the group consisting of hydrogen, CN, CO<sub>2</sub>H, CO<sub>2</sub>R<sup>9</sup>, halogen, NO<sub>2</sub>, OH, SH; OC<sub>1-3</sub> alkyl, the OC<sub>1-3</sub> alkyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, C<sub>6</sub> aryl or NR<sup>11</sup>R<sup>12</sup>; NR<sup>11</sup>R<sup>12</sup> ; C<sub>1-3</sub> alkyl, the C<sub>1-3</sub> alkyl being unsubstituted or substituted by methyl, ethyl, propyl, F, Br, Cl, OH, C<sub>6</sub> aryl or NR<sup>9</sup>R<sup>10</sup>; C<sub>1-3</sub> alkynyl, the C<sub>1-3</sub>-alkynyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, C<sub>6-8</sub> aryl or NR<sup>11</sup>R<sup>12</sup>, preferably unsubstituted ethynyl; SC<sub>1-3</sub> alkyl, the SC<sub>1-3</sub> alkyl being unsubstituted or substituted by methyl, ethyl, propyl, OH, C<sub>6</sub> aryl or NR<sup>9</sup>R<sup>10</sup> and C<sub>6</sub> aryl, the C<sub>6</sub> aryl being unsubstituted or substituted by methyl, ethyl, propyl, OH, NO<sub>2</sub>, CN, F, Br, Cl, C<sub>6</sub> aryl, C<sub>1</sub>-C<sub>3</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or NR<sup>11</sup>R<sup>12</sup>;</dd><dt>R<sup>9</sup>, R<sup>10</sup>, R<sup>11</sup> and R<sup>12</sup></dt><dd>are independently from each other selected from the group consisting of hydrogen, C<sub>1-8</sub> alkyl and C<sub>6-12</sub> aryl, preferably of hydrogen, methyl and ethyl; or</dd><dt>R<sup>11</sup> together with R<sup>12</sup></dt><dd>form together with the N, to which they are connected, a five- or six-membered ring, which may contain further 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S, preferably a morpholino ring.</dd></dl>
0024Especially preferably, the compounds of formula (I) are selected from the group consisting of compounds of formulae (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17), (18), (19), (20), (21), (22), (23), (24), (25), (26), (27), (28), (29), (30), (31), (32), (33), (34) and (35). <chemistry id="chem0013" num="0013"><img file="EP1925643A1_D0013.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP1925643A1_D0014.tif" /></chemistry><chemistry id="chem0015" num="0015"><img file="EP1925643A1_D0015.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP1925643A1_D0016.tif" /></chemistry><chemistry id="chem0017" num="0017"><img file="EP1925643A1_D0017.tif" /></chemistry><chemistry id="chem0018" num="0018"><img file="EP1925643A1_D0018.tif" /></chemistry><chemistry id="chem0019" num="0019"><img file="EP1925643A1_D0019.tif" /></chemistry><chemistry id="chem0020" num="0020"><img file="EP1925643A1_D0020.tif" /></chemistry><chemistry id="chem0021" num="0021"><img file="EP1925643A1_D0021.tif" /></chemistry><chemistry id="chem0022" num="0022"><img file="EP1925643A1_D0022.tif" /></chemistry><chemistry id="chem0023" num="0023"><img file="EP1925643A1_D0023.tif" /></chemistry><chemistry id="chem0024" num="0024"><img file="EP1925643A1_D0024.tif" /></chemistry><chemistry id="chem0025" num="0025"><img file="EP1925643A1_D0025.tif" /></chemistry><chemistry id="chem0026" num="0026"><img file="EP1925643A1_D0026.tif" /></chemistry><chemistry id="chem0027" num="0027"><img file="EP1925643A1_D0027.tif" /></chemistry><chemistry id="chem0028" num="0028"><img file="EP1925643A1_D0028.tif" /></chemistry><chemistry id="chem0029" num="0029"><img file="EP1925643A1_D0029.tif" /></chemistry><chemistry id="chem0030" num="0030"><img file="EP1925643A1_D0030.tif" /></chemistry><chemistry id="chem0031" num="0031"><img file="EP1925643A1_D0031.tif" /></chemistry>
Preparation of the compounds of formula (I)
0025The compounds of formula (I) are prepared by complexing reaction of one equivalent of a compound of formula (Ia) and one equivalent of a compound of formula (IIa) or (IIIa) with one equivalent of a divalent metal salt, <chemistry id="chem0032" num="0032"><img file="EP1925643A1_D0032.tif" /></chemistry> wherein <dl id="dl0013" compact="compact"><dt>R<sup>80</sup>, R<sup>81</sup>, R<sup>82</sup> and R<sup>83</sup></dt><dd>are independently from each other C<sub>1-8</sub> alkyl or C<sub>3-8</sub> cycloalkyl; or</dd><dt>R<sup>80</sup> and R<sup>81</sup></dt><dd>together with the C atom to which they are connected according to formula (I), or, independently from R<sup>80</sup> and R<sup>81</sup> R<sup>82</sup> and R<sup>83</sup> together with the C atom to which they are connected according to formula (II), form a five or six membered aromatic or heteroaromatic cycle, the heteroaromatic cycle containing 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S; the aromatic or heteroaromatic cycle or the C<sub>3-8</sub> cycloalkyl can be annealed with a five or six membered aromatic or heteroaromatic cycle, this second heteroaromatic cycle containing 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S; the C<sub>1-8</sub> alkyl chains, the C<sub>3-8</sub> cycloalkyl, the aromatic or the heteroaromatic cycles can be substituted by 1 to 8 substituents, the substituents being independently from each other selected from the group consisting of hydrogen, CN, CO<sub>2</sub>H, CO<sub>2</sub>R<sup>9</sup>, halogen, NO<sub>2</sub>, OH, SH; C<sub>1-12</sub> alkyl, the C<sub>1-12</sub>-alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>1</sub>-C<sub>8</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or C<sub>6-12</sub> aryl, this C<sub>6-12</sub> aryl residue being unsubstitued or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; C<sub>1-8</sub> alkynyl, the C<sub>1-8</sub> alkynyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>9</sup>R<sup>10</sup>; C<sub>6</sub>-C<sub>12</sub> aryl, the C<sub>6-12</sub> aryl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy, NR<sup>9</sup>R<sup>10</sup> or NR<sup>11</sup>R<sup>12</sup>; C<sub>6-12</sub>-aryl-C<sub>1-12</sub>-alkyl, the C<sub>6-12</sub>-aryl-C<sub>1-12</sub>-alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>9</sup>R<sup>10</sup>; OC<sub>1-8</sub> alkyl, the OC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>11</sup>R<sup>12</sup>; NR<sup>11</sup>R<sup>12</sup>; and SC<sub>1-8</sub> alkyl, the SC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>9</sup>R<sup>10</sup>;</dd><dt>E</dt><dd>together with the two C atoms, to which the Y is double bonded and the squaric acid moiety is single bonded in formula (III), is a five or six membered aromatic or heteroaromatic cycle, the aromatic or heteroaromatic cycle can be annealed with a five or six membered aromatic or heteroaromatic cycle, the heteroaromatic cycles contain independently from each other 1, 2 or 3 heteroatoms selected from the group consisting of O, N and S, the aromatic or heteroaromatic cycles can independently from each other be further substituted by 1 to 6 substituents, the substituents being independently from each other selected from the group consisting of hydrogen, CN, halogen, NO<sub>2</sub>, OH, SH, C<sub>1-8</sub> alkyl, the C<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, halogen, OH, C<sub>6-12</sub> aryl or NR<sup>30</sup>R<sup>31</sup> ; C<sub>6</sub>-C<sub>1</sub> aryl, the C<sub>6-12</sub> aryl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>30</sup>R<sup>31</sup>; C<sub>6-12</sub>-aryl-C<sub>1-12</sub>-alkyl, the C<sub>6-12</sub>-aryl-C<sub>1-12</sub>-alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, NO<sub>2</sub>, CN, halogen, C<sub>6-12</sub> aryl, C<sub>1</sub>-C<sub>8</sub> alkoxy or NR<sup>30</sup>R<sup>31</sup> ; OC<sub>1-8</sub> alkyl, the OC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or NR<sup>32</sup>R<sup>33</sup> ; NR<sup>32</sup>R<sup>33</sup>; and SC<sub>1-8</sub> alkyl, the SC<sub>1-8</sub> alkyl being unsubstituted or substituted by C<sub>1-8</sub> alkyl, OH, C<sub>6-12</sub> aryl or-NR<sup>30</sup>R<sup>31</sup>;</dd><dt>R<sup>9</sup>, R<sup>10</sup>, R<sup>11</sup>, R<sup>12</sup>, R<sup>30</sup>, R<sup>31</sup>, R<sup>32</sup> and R<sup>33</sup></dt><dd>are independently from each other selected from the group consisting of hydrogen, C<sub>1-8</sub> alkyl and C<sub>6-12</sub> aryl; or</dd><dt>R<sup>11</sup> together with R<sup>12</sup>,</dt><dd>or, independently from R<sup>11</sup> and R<sup>12</sup>, R<sup>32</sup> together with R<sup>33</sup> form together with the N, to which they are connected, a five- or six-membered ring, which may contain further 1, 2 or 3 heteroatoms independently from each other selected from the group consisting of O, N and S;</dd><dt>X</dt><dd>is selected from the group consisting of O, S and imino-nitrogen N-R<sup>1</sup>;</dd><dt>Y</dt><dd>is selected from the group consisting of O, S and imino-nitrogen N-R<sup>2</sup>;</dd><dt>R<sup>1</sup> and R<sup>2</sup></dt><dd>are independently from each other selected from the group consisting of hydrogen, C<sub>1-12</sub> alkyl, benzyl and C<sub>6-12</sub> aryl; the C<sub>1-12</sub> alkyl being unsubstituted or substituted by OH, C<sub>6-12</sub> aryl, halogen or NR<sup>30</sup>R<sup>31</sup>.</dd></dl>
0026Preferably, the divalent metal salt is derived from a metal selected from main groups 1 to 5 or from transition groups 1 or 2 or 4 to 8 of the Periodic Table of the Chemical Elements. More preferably, the divalent metal salt is derived from a metal selected from the group consisting of Ca, Sr, Ba, Al, Ga, In, Sc, Y, Ti, Zr, V(O), Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, even more preferably of Al, Y, Zr, V(O), Cr, Mn, Fe, Co, Ni, Cu, Zn and Yb, especially preferably of V(O), Cr, Mn, Co, Fe, Ni, Cu, and Zn. Salts of the divalent metal are preferably acetoacetates, sulfates, halides (preferably fluoride, chloride, bromide, iodide, more preferably chloride and bromide, especially chlorides) and acetates and their respective hydrates.
0027Preferred metal salts are derived from V(O), Fe, Ni, Cu, Co, Zn, and Mn. More preferred metal salts are for example vanadyl-acetoacetate, nickel-, copper-, cobalt-, zinc-, or manganese sulfate; iron-, nickel-, copper-, cobalt-, zinc-, or manganese chloride or iron-, nickel-, copper-, cobalt-, zinc-, or manganese acetate and their respective hydrates, especially the metal salt is selected from the group consisting of Vanadyl(acetoacetate)<sub>2</sub>, Fe(OAc)<sub>2</sub>, Cu(SO<sub>4</sub>), Cu(SO<sub>4</sub>)*5 H<sub>2</sub>O, CuCl<sub>2</sub>, Ni(OAc)<sub>2</sub>*4 H<sub>2</sub>O, NiCl<sub>2</sub>*6 H<sub>2</sub>O, Co(SO<sub>4</sub>), CoSO<sub>4</sub>*7H<sub>2</sub>O, Mn (OAc)<sub>2</sub>*4 H<sub>2</sub>O and Zn(OAc)<sub>2</sub>*4 H<sub>2</sub>O.
0028In the following text, the compounds of formula (Ia) and (IIa) are also called Schiff base ligands; and the compounds of formula (IIIa) are also called squaric acid ligands.
0029The complexing reaction is preferably done at temperatures of from-10°C to 200°C, preferably of from 0°C to 130°C, more preferably of from 20°C to 120°C, even more preferably the complexing reaction is carried out between room temperature and reflux temperature and at atmospheric pressure.
0030The reaction time of complexing reaction is preferably between 1 min and 24 h, more preferably between 10 min and 12 h, even more preferably between 15 min and 6 h.
0031Preferably, the compounds of formula (I) are prepared by complexing reaction of a solution of one equivalent of a metal salt with a boiling solution of one equivalent of the compounds of formula (Ia) and one equivalent of the compounds of formula (IIa) and/or of formula (IIIa) respectively. It is possible to use more than one compound of formula (Ia), as well as more than one compound of formula (IIa) and/or (IIIa) respectively. Preferably the combined amounts of the compounds of formula (Ia) and (IIa) and/or (IIIa) should preferably be equal to two equivalents of the metal salt. Of course it is also possible to use more than one metal salt, preferably a mixture of 2 or 3 metal salts, in the required stoichiometric amounts with regard to the compounds of fomula (Ia) and (IIa) and/or (IIIa); and a combination of these measures is also possible.
0032The complexing reaction usually results in a precipitate, the precipitate is isolated following standard methods, preferably by filtration. In case of a solution, the solvent can be removed until precipitation occurs, or the solution is combined with another solvent to initiate precipitation, preferably with water and/or hexane or toluene, and then the product is isolated by filtration.
0033The solvents that can be used in the complexing reaction are water, organic solvents and mixtures thereof. The solvents are preferably selected from the group consisting of C<sub>1-8</sub> alcohols, nitriles, preferably acetonitrile, acetone, aromatic solvents such as toluene or chlorobenzene, DMF, DMSO, NMP, pyridine.
0034More preferred solvents used for the complexing reaction are C<sub>1-8</sub> alcohols, nitriles an pyridine, especially ethanol, pyridine and acetonitrile.
0035It is also possible to add the metal salt already at an earlier stage of the synthesis of the compounds of formula (Ia), (IIa) and/or (IIIa) or their precursors, preferably before, during or after the Schiff base forming reaction, more preferably after the Schiff base forming reaction, to the resulting suspension or solution of the Schiff base ligand.
0036Even more preferably the Schiff base ligands are isolated and dried after synthesis, and the complexing reaction is carried out in a separate step.
Preparation of the Schiff base ligands of formula (Ia) and (IIa)
0037The Schiff base ligands of the formula (Ia) and (IIa) are prepared by condensation reaction of the respective compounds of formula (Iaa) or (IIaa), also called amine components or the respective amines, with 2-Hydroxy-5-nitrobenzaldehyde; <chemistry id="chem0033" num="0033"><img file="EP1925643A1_D0033.tif" /></chemistry> wherein R80, R81, R82 and R83 have the same meaning as described above with all their preferred embodiments. These respective amines, i.e. the compounds of formula (Iaa) or (IIaa), and 2-Hydroxy-5-nitrobenzaldehyde are known substances and can be prepared according to known procedures.
0038It is possible to use more than one amine component, resulting in the respective mixture of Schiff base ligands.
0039The condensation reaction preferably is carried out in an organic acid. The organic acid is more preferably selected from the group consisting of formic acid, acetic acid, propionic acid and mixtures thereof, more preferably acetic acid is used.
0040Also preferably the condensation reaction is carried out in a solvent, more preferably in water, in organic solvents or in mixtures thereof. The solvents are preferably selected from the group consisting of C<sub>1-8</sub> alcohols, nitriles, preferably acetonitrile, acetone, aromatic solvents such as toluene or chlorobenzene, DMF, DMSO, NMP, pyridine.
0041More preferred solvents used for the condensation reaction are C<sub>1-8</sub> alcohols and aromatic solvents, especially ethanol and toluene.
0042The condensation reaction is preferably carried out in a stoichiometric ratio between the 2-Hydroxy-5-nitrobenzaldehyde and the amine component. The condensation reaction is preferably done at temperatures between -10°C to 200°C, preferably between 0°C to 130°C, more preferably between 15°C to 120°C, even more preferably the condensation reaction is carried out between room temperature and reflux temperature and at atmospheric pressure. It is also possible to strip off the solvent during condensation reaction to remove water from the reaction mixture. Preferably, this is done by a solvent that forms an azeotropic mixture with water, preference being given to ethanol and toluene and mixtures thereof, particular preference to ethanol. The condensation reaction is preferably catalysed by acids, more preferably by organic acids, even more preferably by formic acid, acetic acid, propionic acid, para-toluene sulfonic acid and mixtures thereof, especially preferably by acetic acid and para-toluene sulfonic acid.
0043Preferably, the Schiff base ligand is isolated following standard methods, in case of a precipitate preferably by filtration, and preferably dried. In case of a solution, the solvent can be removed until precipitation occurs or the solution is combined with another solvent to initiate precipitation, preferably with aliphatic or aromatic solvents, more preferably hexane and toluene, and then the product is isolated by filtration.
Preparation of the squaric acid ligands of formula (IIIa)
0044The compounds of formula (IIIa) are known compounds and can be produced according to or in analogy to known procedures.
0045A further subject of the invention is therefore a process for the preparation of the compounds of formula (I), as well as of the compounds of formula (I) in all the preferred aspects of the formula (I) as described above, by a complexing reaction of the ligands of formula (Ia) and (IIa) and/or (IIIa), with a metal salt; with the compounds of formula (Ia) and (IIa) preferably being prepared by a condensation reaction of the 2-Hydroxy-5-nitrobenzaldehyde with the respective amines.
0046Another subject of the invention is a compound of formula (105), (106), (109), (110) or (112). <chemistry id="chem0034" num="0034"><img file="EP1925643A1_D0034.tif" /></chemistry><chemistry id="chem0035" num="0035"><img file="EP1925643A1_D0035.tif" /></chemistry><chemistry id="chem0036" num="0036"><img file="EP1925643A1_D0036.tif" /></chemistry>
0047Another subject of the invention is a process for the preparation of a compound of formula (105), (106), (109), (110) or (112) by condensation reaction of the respective amine with 2-Hydroxy-5-nitrobenzaldehyde. The preferred embodiments of this condensation reaction are those described above under the heading "Preparation of the Schiff base ligands of formula (Ia) and (IIa)"
0048A further subject of the invention is the use of a compound of a formula selected from the group of formulae (105), (106), (109), (110) and (112), as a ligand, preferably as a ligand in metal complex dyes; the metal complex dyes preferably being used in optical layers, more preferably in optical layers for optical data recording.
0049A further subject of the invention is the use of the compounds of formula (I) and the use of the compounds of formula (I) in all the preferred aspects of the formula (I) as described above, in an optical layer, preferably in an optical layer for optical data recording.
0050A further subject of the invention is the use of the compounds of formula (I) and the use of the compounds of formula (I) in all the preferred aspects of the formula (I) as described above, as a dye in an optical layer, preferably in an optical layer for optical data recording.
0051A further subject of the present invention is an optical layer comprising at least one compound of formula (I) in all the preferred aspects of the formula (I) as described above, and the use of said optical layer for optical data recording media. An optical layer according to the invention may also comprise a mixture of two or more, preferably of two or three, more preferably of two compounds of formula (I). A further subject of the invention therefore is an optical data recording medium comprising an optical layer comprising at least one compound of formula (I) in all the preferred aspects of the formula (I) as described above.
0052Further, the invention relates to a method for producing optical layers on a substrate comprising the following steps <ol id="ol0001" compact="compact" ol-style=""><li>(a) providing a substrate,</li><li>(b) dissolving at least one compound of formula (I) in an organic solvent to form a solution,</li><li>(c) coating the solution (b) on the substrate (a),</li><li>(d) evaporating the solvent to form an optical layer (also called dye layer or recording layer).</li></ol>
(a) Substrate
0053The substrate, which functions as support for the layers applied thereto, is advantageously semi-transparent (transmittance T>10%) or preferably transparent (transmittance T>90%). The support can have a thickness of from 0.01 to 10 mm, preferably from 0.1 to 5 mm. Suitable substrates are, for example, glass, minerals, ceramics and thermosetting or thermoplastic plastics. Preferred supports are glass and homo- or co-polymeric plastics. Suitable plastics are, for example, thermoplastic polycarbonates, polyamides, polyesters, polyacrylates and polymethacrylates, polyurethanes, polyolefins, polyvinyl chloride, polyvinylidene fluoride, polyimides, thermosetting polyesters and epoxy resins. The most preferred substrates are polycarbonate (PC) or polymethylmethacrylate (PMMA).
0054The substrate can be in pure form or may also comprise customary additives, for example UV absorbers as light-stabilizers for the optical layer.
0055The substrate is advantageously transparent over at least a portion of the range from 350 to 500 nm, so that it is permeable to at least 90% of the incident light of the writing or readout wavelength.
(b) Organic solvents
0056Organic solvents are selected from C<sub>1-8</sub> alcohol, halogen substituted C<sub>1-8</sub> alcohols, C<sub>1-8</sub> ketone, C<sub>1-8</sub> ether, halogen substituted C<sub>1-4</sub> alkane, nitriles, preferably acetonitrile, or amides, or mixtures thereof. Preferred C<sub>1-8</sub> alcohols or halogen substituted C<sub>1-8</sub> alcohols are for example methanol, ethanol, isopropanol, diacetone alcohol (DAA), 2,2,3,3-tetrafluoropropanol, trichloroethanol, 2-chloroethanol, octafluoropentanol or hexafluorobutanol, more preferred 2,2,3,3-tetrafluoro-1-propanol. Preferred C<sub>1-8</sub> ketones are for example acetone, methylisobutylketone, methylethylketone, or 3-hydroxy-3-methyl-2-butanone. Preferred halogen substituted C<sub>1-4</sub> alkanes are for example chloroform, dichloromethane or 1-chlorobutane. Preferred amides are for example dimethylformamide or dimethylacetamide.
(c) Coating methods
0057Suitable coating methods are, for example, immersion, pouring, brush-coating, blade-application and spin-coating, as well as vapor-deposition methods carried out under a high vacuum. When pouring methods are used, solutions in organic solvents are generally used. When solvents are employed, care should be taken that the supports used are insensitive to those solvents. The optical layer is preferably applied by spin-coating with a dye solution.
(d) Optical layer (also called dye layer or recording layer)
0058The optical layer is preferably arranged between the transparent substrate and the reflecting layer. The thickness of the recording layer is from 10 to 1000 nm, preferably from 30 to 300 nm, more preferably from 70 to 250 nm, especially about 80 nm, for example from 60 to 120 nm. The optical layer comprises at least one compound of formula (I) preferably in an amount sufficient to have a substantial influence on the refractive index, for example at least 30% by weight of the total weight of the optical layer, more preferably at least 60% by weight, most preferably at least 80% by weight. Further customary components are stabilizers, for example <sup>1</sup>0<sub>2</sub>-, triplet- or luminescence quenchers, melting-point reducers, decomposition accelerators or any other additives that have already been described in optical data recording media. Preferably, stabilizers or fluorescence-quenchers are added if desired. Stabilizers, <sup>1</sup>0<sub>2</sub>-, triplet- or luminescence-quenchers are, for example, metal complexes of N- or S-containing enolates, phenolates, bisphenolates, thiolates or bisthiolates, hindered phenols and derivatives thereof such as o-hydroxyphenyl-triazoles or -triazines or other UV absorbers, such as hindered amines (TEMPO or HALS, as well as nitroxides or NOR-HALS), and also as cations diimmonium, Paraquat<sup>™</sup> or Orthoquat salts, such as <sup>®</sup>Kayasorb IRG 022, <sup>®</sup>Kayasorb IRG 040, optionally also as radical ions, such as N,N,N',N'-tetrakis(4-dibutylaminophenyl)-p-phenylene amine-ammonium hexafluorophosphate, hexafluoroantimonate or perchlorate. The latter are available from Organica (Wolfen/DE); <sup>®</sup>Kayasorb brands are available from Nippon Kayaku Co. Ltd.
0059In a preferred aspect, the present invention provides for an optical layer suitable for high-density recording material, e.g. of the WORM disc format, in a laser wavelength range of from 350-450nm, preferably around 405 nm.
Preparation of the optical data recording medium
0060A method for producing an optical data recording medium comprising an optical layer according to the invention usually comprises the following additional steps <ul id="ul0001" list-style="none" compact="compact"><li>(e) applying a metal layer (also called reflective layer) onto the optical layer,</li><li>(f) applying a second polymer based layer to complete the disk (cover layer or protective layer).</li></ul>
(e) Reflective layer
0061The application of the metallic reflective layer is preferably effected by sputtering, vapor-deposition in vacuum or by chemical vapor deposition (CVD). The sputtering technique is especially preferred for the application of the metallic reflective layer. Reflecting materials suitable for the reflective layer include especially metals, which provide good reflection of the laser radiation used for recording and playback, for example the metals of Main Groups III, IV and V and of the Sub-groups of the Periodic Table of the Elements. Al, In, Sn, Pb, Sb, Bi, Cu, Ag, Au, Zn, Cd, Hg, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu and alloys thereof are especially suitable. Special preference is given to a reflective layer of aluminum, silver, copper, gold or an alloy thereof, on account of their high reflectivity and ease of production.
(f) Cover layer (also called protective layer)
0062Materials suitable for the cover layer include plastics, which are applied in a thin layer to the support or the uppermost layer either directly or with the aid of adhesive layers. The material of the cover layer may for example be the same as the material of the substrate. It is advantageous to select mechanically and thermally stable plastics having good surface properties, which may be modified further. The plastics may be thermosetting plastics and thermoplastic plastics. Preference is given to radiation-cured (e.g. using UV radiation) protective layers, which are particularly simple and economical to produce. A wide variety of radiation-curable materials are known. Examples of radiation-curable monomers and oligomers are acrylates and methacrylates of diols, triols and tetrols, polyimides of aromatic tetracarboxylic acids and aromatic diamines having C<sub>1</sub>-C<sub>4</sub>alkyl groups in at least two ortho-positions of the amino groups, and oligomers with dialkylmaleinimidyl groups, e.g. dimethyl maleinimidyl groups.
0063A high-density optical data recording medium according to the invention therefore preferably is a recordable optical disc comprising: a first substrate, which is a transparent substrate with grooves, a optical layer (recording layer), which is formed on the first substrate surface using at least one compound of formula (I) a reflective layer formed on the optical layer, a second substrate, which is a transparent substrate connected to the reflective layer with an attachment layer.
0064The optical data recording medium according to the invention is preferably a recordable optical disc of the WORM type. It may be used, for example, as a playable HD-DVD (high density digital versatile disc) or Blu-ray<sup>®</sup> disc, as storage medium for a computer or as an identification and security card or for the production of diffractive optical elements, for example holograms.
0065The optical data recording media according to the invention may also have additional layers, for example interference layers. It is also possible to construct optical data recording media having a plurality of (for example two) recording layers. The structure and the use of such materials are known to the person skilled in the art. Preferred, if present, are interference layers that are arranged between the recording layer and the reflecting layer and/or between the recording layer and the substrate and consist of a dielectric material of TiO<sub>2</sub>, Si<sub>3</sub>N<sub>4</sub>, ZnS or silicone resins. These optical data recording media according to the invention can be produced by processes known in the art.
Readout methods
0066The structure of the optical data recording medium according to the invention is governed primarily by the readout method; known function principles include the measurement of the change in the transmission or, preferably, in the reflection, but it is also known to measure, for example, the fluorescence instead of the transmission or reflection. When the optical data recording medium is structured for a change in reflection, the following structures can be used: transparent support / recording layer (optionally multilayered) / reflective layer and, if expedient, protective layer (not necessarily transparent); or support (not necessarily transparent) / reflective layer / recording layer and, if expedient, transparent protective layer. In the first case, the light is incident from the support side, whereas in the latter case the radiation is incident from the recording layer side or, where applicable, from the protective layer side. In both cases the light detector is located on the same side as the light source. The first-mentioned structure of the recording material to be used according to the invention is generally preferred. When the optical data recording medium is structured for a change in light transmission, the following different structure comes into consideration: transparent support/recording layer (optionally multilayered) and, if expedient, transparent protective layer. The light for recording and for readout can be incident either from the support side or from the recording layer side or, where applicable, from the protective layer side, the light detector in this case always being located on the opposite side. Suitable lasers are those having a wavelength of 350-500 nm, for example commercially available lasers having a wavelength of 405 to 414 nm, especially semi-conductor lasers. The recording is done, for example, point for point, by modulating the laser in accordance with the mark lengths and focusing its radiation onto the recording layer. It is known from the specialist literature that other methods are currently being developed which may also be suitable for use. The process according to the invention allows the storage of information with great reliability and stability, distinguished by very good mechanical and thermal stability and by high light stability and by sharp boundary zones of the pits. Special advantages include the high contrast, the low jitter and the surprisingly high signal/noise ratio, so that excellent readout is achieved. The readout of information is carried out according to methods known in the art by registering the change in absorption or reflection using laser radiation.
0067The invention accordingly relates also to a method for the optical data recording, storage and playback of information, wherein an optical data recording medium according to the invention is used. The recording and the playback advantageously take place in a wavelength range of from 350 to 500 nm.
0068The compounds of formula (I) provide for particularly preferable properties when used in optical layers for optical data recording media according to the invention. They possess the required optical characteristics, demonstrated when used in the form of a solid film: <ul id="ul0002" list-style="bullet" compact="compact"><li>an advantageously homogeneous, amorphous and low-scattering optical layer,</li><li>a high refractive index at the longer wavelength flank of the absorption band, which preferably achieves n values of the refractive index of from 1.0 to 3.0 in the range of from 340 to 500 nm,</li><li>a high sensitivity under laser radiation of high power density and good playback characteristics in the desired spectral range,</li><li>an enhanced photosensitivity and stability (in daylight and under laser radiation of low power density) compared to dyes already known in the art,</li><li>an uniform script width and a high contrast,</li><li>an absorption maximum λmax in the preferred range between 340 nm and 470 nm as being preferred for blue laser applications, more precisely from 340 to 390 nm,</li><li>a decomposition point (DP) in the preferred temperature range between 220°C and 350°C, more precisely 240°C to 340°C,</li><li>a sufficient heat release (HR).</li></ul>
0069Recording performance of a compound is related to specific parameters measured on disc like: <ul id="ul0003" list-style="bullet" compact="compact"><li>a high reflectivity (R),</li><li>a low laser recording power (Pw or OPC: optimum power control),</li><li>good readout stability at several laser reading powers,</li><li>an appropriate carrier to noise ratio (CNR).</li></ul>
0070The absorption edge is surprisingly steep even in the solid phase.
0071The compounds of formula (I) also show a narrow decomposition temperature of 220-350°C, fitting with the thermal requirements. Additionally, these compositions show a high solubility in organic solvents, which is ideal for the spin-coating process to manufacture optical layers.
Examples
UV-vis
0072For UV-vis spectra, λ max and ε values of a compound are determined by using an UV-vis spectrophotometer, the compositions were dissolved in CH<sub>2</sub>Cl<sub>2</sub>, DMSO or in tfp. The values are obtained by balancing the measurements performed on compound solutions at three different concentrations.
Thermal Decomposition: Decomposition point (DP) and heat release (HR)
0073For the determination of DP and HR, the compound or the composition is incorporated into a sealed aluminum pan. Analysis conditions are as following: Temperature range from 25 to 400°C, heating rate 10°C/min, nitrogen flow of 50 ml/min. Values are determined by single measurement.
Melting point (MP)
0074For the determination of melting point, the compound or the composition is incorporated in a glass capillary. The capillary was heated using the following profile: temperature range from 20 to 350 °C, heating rate 2 °C/min.
Carrier to noise ratio (CNR)
0075CNR is a measure of signal strength relative to background noise. The ratio is measured in decibels (dB). CNR is measured in a state in which information has been recorded in the adjacent tracks. The higher the CNR the better is the signal resolution.
Reflectivity (R)
0076A definition and the measuring techniques for the light reflectivity (R) is described in a book available from DVD Format Logo Licensing Co., Ltd. for example, Annex D of Version 0.9, PART 1 Physical Specifications, DVD Specifications for High Density Read-Only Disk.
Example 102
0077To a suspension of a 5.0 g of 2-Hydroxy-5-nitrobenzaldehyde in 50 mL of ethanol were added 6.1 g of 4-Amino-antipyrine (called "the amine" in the following text) at room temperature. Immediately after addition a thick, yellow suspension was formed. The suspension was refluxed for 1 h. After cooling to room temperature, the suspension was filtered, washed with 20 mL of ethanol and dried in vacuum at 80 °C for 4 h. 10.1 g of a compound of formula (102) are obtained. Analytical data for compound of formula (102): λ max = 365 nm, ε = 63 L/g*cm MP: 198 °C <chemistry id="chem0037" num="0037"><img file="EP1925643A1_D0037.tif" /></chemistry>
Examples (103) to (112)
0078The ligand synthesis was repeated according to example (102) with 2-hydroxy-5-nitrobenzaldehyde and with the respective amine to yield compounds of formulae (103) to (112). The combinations and details are given in tables (A1) and (A2). In the case of examples (111) and (112), to the reaction mixture were added 0.5 mL of acetic acid before heating to reflux. <chemistry id="chem0038" num="0038"><img file="EP1925643A1_D0038.tif" /></chemistry><chemistry id="chem0039" num="0039"><img file="EP1925643A1_D0039.tif" /></chemistry><chemistry id="chem0040" num="0040"><img file="EP1925643A1_D0040.tif" /></chemistry><tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="11mm" /><colspec colnum="2" colname="col2" colwidth="53mm" /><colspec colnum="3" colname="col3" colwidth="10mm" /><colspec colnum="4" colname="col4" colwidth="55mm" /><colspec colnum="5" colname="col5" colwidth="19mm" /><colspec colnum="6" colname="col6" colwidth="19mm" /><thead><row><entry namest="col1" nameend="col6" align="center" valign="top"><b>Table (A1)</b></entry></row><row><entry align="center" valign="top"><b>Ex.</b></entry><entry align="center" valign="top"><b>2-Hydroxy-5-nitro-benzaldehyde</b></entry><entry namest="col3" nameend="col4" align="center" valign="top"><b>the amine</b></entry><entry namest="col5" nameend="col6" align="center" valign="top"><b>Compound of formula</b></entry></row><row><entry align="center" valign="top" /><entry align="center" valign="top"><b>[g]</b></entry><entry align="center" valign="top"><b>[g]</b></entry><entry align="center" valign="top" /><entry align="center" valign="top"><b>[g]</b></entry><entry align="center" valign="top" /></row></thead><tbody><row><entry align="center"><b>102</b></entry><entry align="center">5.0</entry><entry align="center">6,1</entry><entry align="center">4-Amino-antipyrine</entry><entry align="center">10,1</entry><entry align="center">(102)</entry></row><row><entry align="center"><b>103</b></entry><entry align="center">5.0</entry><entry align="center">5,5</entry><entry align="center">4-(N-morpholino) aniline</entry><entry align="center">9,4</entry><entry align="center">(103)</entry></row><row><entry align="center"><b>104</b></entry><entry align="center">6,7</entry><entry align="center">4,9</entry><entry align="center">2-Diethylamino-ethylamine</entry><entry align="center">8,9</entry><entry align="center">(104)</entry></row><row><entry align="center"><b>105</b></entry><entry align="center">6,7</entry><entry align="center">6.0</entry><entry align="center">3-Morpholino-propylamine</entry><entry align="center">9.0</entry><entry align="center">(105)</entry></row><row><entry align="center"><b>106</b></entry><entry align="center">3,4</entry><entry align="center">2,8</entry><entry align="center">2-Morpholino-ethylamine</entry><entry align="center">5,3</entry><entry align="center">(106)</entry></row><row><entry align="center"><b>107</b></entry><entry align="center">3,4</entry><entry align="center">1,2</entry><entry align="center">Cyclopropylamine</entry><entry align="center">3,5</entry><entry align="center">(107)</entry></row><row><entry align="center"><b>108</b></entry><entry align="center">3,4</entry><entry align="center">1,8</entry><entry align="center">Cyclopentylamine</entry><entry align="center">2,9</entry><entry align="center">(108)</entry></row><row><entry align="center"><b>109</b></entry><entry align="center">1.0</entry><entry align="center">1,1</entry><entry align="center">Methyl-2-aminothiophene- 3-carboxylate</entry><entry align="center">1,6</entry><entry align="center">(109)</entry></row><row><entry align="center"><b>110</b></entry><entry align="center">1,4</entry><entry align="center">1.0</entry><entry align="center">2-Ethynyl-aniline</entry><entry align="center">2.0</entry><entry align="center">(110)</entry></row><row><entry align="center"><b>111</b></entry><entry align="center">1,4</entry><entry align="center">1.0</entry><entry align="center">3-Ethynyl-aniline</entry><entry align="center">2.0</entry><entry align="center">(111)</entry></row><row><entry align="center"><b>112</b></entry><entry align="center">1,4</entry><entry align="center">1.0</entry><entry align="center">4-Ethynyl-aniline</entry><entry align="center">2.0</entry><entry align="center">(112)</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="11mm" /><colspec colnum="2" colname="col2" colwidth="19mm" /><colspec colnum="3" colname="col3" colwidth="28mm" /><colspec colnum="4" colname="col4" colwidth="23mm" /><colspec colnum="5" colname="col5" colwidth="38mm" /><thead><row><entry namest="col1" nameend="col5" align="center" valign="top"><b>Table (A2)</b></entry></row><row><entry align="center" valign="top"><b>Ex.</b></entry><entry align="center" valign="top"><b>λ<sub>max</sub> [nm]</b></entry><entry align="center" valign="top"><b>ε(λ<sub>max</sub>) [L/g/cm]</b></entry><entry align="center" valign="top"><b>MP/DP [°C]</b></entry><entry align="center" valign="top"><b>Compound of formula</b></entry></row></thead><tbody><row><entry align="center"><b>102</b></entry><entry align="center">365</entry><entry align="center">63</entry><entry align="center">198 (MP)</entry><entry align="center">(102)</entry></row><row><entry align="center"><b>103</b></entry><entry align="center">382</entry><entry align="center">73</entry><entry align="center">227 (MP)</entry><entry align="center">(103)</entry></row><row><entry align="center"><b>104</b></entry><entry align="center">414</entry><entry align="center">57</entry><entry align="center">115 (MP)</entry><entry align="center">(104)</entry></row><row><entry align="center"><b>105</b></entry><entry align="center">409</entry><entry align="center">54</entry><entry align="center">130 (MP)</entry><entry align="center">(105)</entry></row><row><entry align="center"><b>106</b></entry><entry align="center">420</entry><entry align="center">62</entry><entry align="center">153 (MP)</entry><entry align="center">(106)</entry></row><row><entry align="center"><b>107</b></entry><entry align="center">317</entry><entry align="center">51</entry><entry align="center">100 (MP)</entry><entry align="center">(107)</entry></row><row><entry align="center"><b>108</b></entry><entry align="center">406</entry><entry align="center">54</entry><entry align="center">110 (MP)</entry><entry align="center">(108)</entry></row><row><entry align="center"><b>109</b></entry><entry align="center">383</entry><entry align="center">48</entry><entry align="center">240 (DP)</entry><entry align="center">(109)</entry></row><row><entry align="center"><b>110</b></entry><entry align="center">350</entry><entry align="center">51</entry><entry align="center">174 (MP)</entry><entry align="center">(110)</entry></row><row><entry align="center"><b>111</b></entry><entry align="center">447</entry><entry align="center">33</entry><entry align="center">196 (MP)</entry><entry align="center">(111)</entry></row><row><entry align="center"><b>112</b></entry><entry align="center">449</entry><entry align="center">33</entry><entry align="center">185 (DP)</entry><entry align="center">(112)</entry></row></tbody></tgroup></table></tables>
Example 201
00790.35 g of a compound of formula (102), 0.28 g of a compound of formula (101) and 0.1 g of copper-(II)-acetate monohydrate are suspended in 10 ml of ethanol. After stirring at reflux temperature for 6 h, the suspension is cooled to room temperature and filtered. The remaining yellow residue is washed with 10 mL of ethanol and dried in vacuum at 80 °C for 4 h. 0.66 g of a compound of formula (1) is obtained. Analytical data for compound of formula (1): λ <sub>max</sub> = 346 nm, ε = 57 L/g*cm MP: no melting DP: 281 °C.
Example 202
00800.7 g of a compound of formula (102) and 0.2 g of nickel-(II)-acetate tetrahydrate are suspended in 80 ml of ethanol. After stirring at reflux temperature for 15 min, the greenish suspension is cooled to room temperature and filtered. The remaining yellow residue is washed with 10 mL of ethanol and dried in vacuum at 80 °C for 4 h. 0.7 g of a compound of formula (2) is obtained. Analytical data for compound of formula (2): λ <sub>max</sub> = 370 nm, ε = 56 L/g*cm MP: 229 °C DP: 256 °C.
Examples 203 to 235
0081The complexing reaction according to example 202 was repeated with the respective metal salts and with the respective compounds of formulae (102) to (112), prepared according to examples (102) to (112), to yield compounds of formulae (3) to (35). Refluxing time was 6 h. To the reactions of examples 207, 208, 218, 219 and 221 was added pyridine (Py in table B1) before refluxing, to the reactions of examples 231 and 234 was added acetonitrile (ACN in table B1) before refluxing. The reaction of example (35) was carried out in 10 ml refluxing acetonitrile. The combinations and the details are given in tables (B1) and (B2). Work-up and isolation of product was performed as described in example 202. In the case of examples 209, 210, 220, 222 and 223 the reaction was carried out in pyridine instead of ethanol as solvent. After complete conversion, the resulting reaction mixtures were poured onto 50 mL of water. The residue was washed and dried as described in example 202, yielding the complexes (9), (10), (11), (12) and (13). <tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="10"><colspec colnum="1" colname="col1" colwidth="11mm" /><colspec colnum="2" colname="col2" colwidth="12mm" /><colspec colnum="3" colname="col3" colwidth="21mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><colspec colnum="5" colname="col5" colwidth="22mm" /><colspec colnum="6" colname="col6" colwidth="19mm" /><colspec colnum="7" colname="col7" colwidth="17mm" /><colspec colnum="8" colname="col8" colwidth="21mm" /><colspec colnum="9" colname="col9" colwidth="22mm" /><colspec colnum="10" colname="col10" colwidth="12mm" /><thead><row><entry namest="col1" nameend="col10" align="center" valign="top"><b>Table (B1)</b></entry></row><row><entry align="center" valign="top"><b>Ex.</b></entry><entry align="center" valign="top"><b>M</b></entry><entry namest="col3" nameend="col4" align="center" valign="top"><b>Used Metal salt</b></entry><entry namest="col5" nameend="col6" align="center" valign="top"><b>Ligand(s)</b></entry><entry align="center" valign="top"><b>Ethanol</b></entry><entry align="center" valign="top"><b>Addition Py or ACN</b></entry><entry namest="col9" nameend="col10" align="center" valign="top"><b>Metal complex</b></entry></row><row><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top"><b>[g]</b></entry><entry align="center" valign="top"><b>Compound of formula</b></entry><entry align="center" valign="top"><b>[g]</b></entry><entry align="center" valign="top"><b>[mL]</b></entry><entry align="center" valign="top"><b>[mL]</b></entry><entry align="center" valign="top"><b>Compound of formula</b></entry><entry align="center" valign="top"><b>[g]</b></entry></row></thead><tbody><row><entry align="center"><b>201</b></entry><entry align="center">Cu</entry><entry align="center">Cu(OAc)2</entry><entry align="center">0.1</entry><entry align="center">(102) (101)</entry><entry align="center">0.35 0.28</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(1)</entry><entry align="center">0.66</entry></row><row><entry align="center"><b>202</b></entry><entry align="center">Ni</entry><entry align="center">Ni(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(102)</entry><entry align="center">0.7</entry><entry align="center">15</entry><entry align="center">-</entry><entry align="center">(2)</entry><entry align="center">0,7</entry></row><row><entry align="center"><b>203</b></entry><entry align="center">Cu</entry><entry align="center">Cu(OAc)2</entry><entry align="center">0.8</entry><entry align="center">(103)</entry><entry align="center">3</entry><entry align="center">80</entry><entry align="center">-</entry><entry align="center">(3)</entry><entry align="center">3.3</entry></row><row><entry align="center"><b>204</b></entry><entry align="center">Ni</entry><entry align="center">Ni(OAc)2</entry><entry align="center">1.2</entry><entry align="center">(103)</entry><entry align="center">3</entry><entry align="center">80</entry><entry align="center">-</entry><entry align="center">(4)</entry><entry align="center">3.2</entry></row><row><entry align="center"><b>205</b></entry><entry align="center">Zn</entry><entry align="center">Zn(OAc)2</entry><entry align="center">1</entry><entry align="center">(103)</entry><entry align="center">3</entry><entry align="center">80</entry><entry align="center">-</entry><entry align="center">(5)</entry><entry align="center">3.3</entry></row><row><entry align="center"><b>206</b></entry><entry align="center">Co</entry><entry align="center">Co(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(102)</entry><entry align="center">0.7</entry><entry align="center">25</entry><entry align="center">-</entry><entry align="center">(6)</entry><entry align="center">0.7</entry></row><row><entry align="center"><b>207</b></entry><entry align="center">Cu</entry><entry align="center">Cu(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(102)</entry><entry align="center">0.7</entry><entry align="center">15</entry><entry align="center">0,5 (Py)</entry><entry align="center">(7)</entry><entry align="center">0.6</entry></row><row><entry align="center"><b>208</b></entry><entry align="center">Fe</entry><entry align="center">Fe(OAc)2</entry><entry align="center">0.1</entry><entry align="center">(102)</entry><entry align="center">0.5</entry><entry align="center">15</entry><entry align="center">15 (Py)</entry><entry align="center">(8)</entry><entry align="center">0.5</entry></row><row><entry align="center"><b>209</b></entry><entry align="center">Mn</entry><entry align="center">Mn(OAc)2</entry><entry align="center">0.1</entry><entry align="center">(102)</entry><entry align="center">0.5</entry><entry align="center">-</entry><entry align="center">15 (Py)</entry><entry align="center">(9)</entry><entry align="center">0.3</entry></row><row><entry align="center"><b>210</b></entry><entry align="center">V(O)</entry><entry align="center">V(O)acac2</entry><entry align="center">0.2</entry><entry align="center">(102)</entry><entry align="center">0.5</entry><entry align="center">-</entry><entry align="center">15 (Py)</entry><entry align="center">(10)</entry><entry align="center">0.3</entry></row><row><entry align="center"><b>211</b></entry><entry align="center">Ni</entry><entry align="center">Ni(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(104)</entry><entry align="center">0.5</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(11)</entry><entry align="center">0.6</entry></row><row><entry align="center"><b>212</b></entry><entry align="center">Co</entry><entry align="center">Co(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(104)</entry><entry align="center">0.5</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(12)</entry><entry align="center">0.5</entry></row><row><entry align="center"><b>213</b></entry><entry align="center">Cu</entry><entry align="center">Cu(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(104)</entry><entry align="center">0.5</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(13)</entry><entry align="center">0.4</entry></row><row><entry align="center"><b>214</b></entry><entry align="center">Ni</entry><entry align="center">Ni(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(105)</entry><entry align="center">0.6</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(14)</entry><entry align="center">0.6</entry></row><row><entry align="center"><b>215</b></entry><entry align="center">Co</entry><entry align="center">Co(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(105)</entry><entry align="center">0.6</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(15)</entry><entry align="center">0.6</entry></row><row><entry align="center"><b>216</b></entry><entry align="center">Ni</entry><entry align="center">Ni(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(106)</entry><entry align="center">0.6</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(16)</entry><entry align="center">0.5</entry></row><row><entry align="center"><b>217</b></entry><entry align="center">Co</entry><entry align="center">Co(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(106)</entry><entry align="center">0.6</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(17)</entry><entry align="center">0.5</entry></row><row><entry align="center"><b>218</b></entry><entry align="center">Ni</entry><entry align="center">Ni(OAc)2</entry><entry align="center">0.4</entry><entry align="center">(107)</entry><entry align="center">0.6</entry><entry align="center">15</entry><entry align="center">15 (Py)</entry><entry align="center">(18)</entry><entry align="center">0.7</entry></row><row><entry align="center"><b>219</b></entry><entry align="center">Co</entry><entry align="center">Co(OAc)2</entry><entry align="center">0.4</entry><entry align="center">(107)</entry><entry align="center">0.6</entry><entry align="center">15</entry><entry align="center">15 (Py)</entry><entry align="center">(19)</entry><entry align="center">0.7</entry></row><row><entry align="center"><b>220</b></entry><entry align="center">Cu</entry><entry align="center">Cu(OAc)2</entry><entry align="center">0.3</entry><entry align="center">(107)</entry><entry align="center">0.6</entry><entry align="center">-</entry><entry align="center">15 (Py)</entry><entry align="center">(20)</entry><entry align="center">0.6</entry></row><row><entry align="center"><b>221</b></entry><entry align="center">Ni</entry><entry align="center">Ni(OAc)2</entry><entry align="center">0.4</entry><entry align="center">(108)</entry><entry align="center">0.7</entry><entry align="center">15</entry><entry align="center">15 (Py)</entry><entry align="center">(21)</entry><entry align="center">0.7</entry></row><row><entry align="center"><b>222</b></entry><entry align="center">Co</entry><entry align="center">Co(OAc)2</entry><entry align="center">0.4</entry><entry align="center">(108)</entry><entry align="center">0.7</entry><entry align="center">-</entry><entry align="center">15 (Py)</entry><entry align="center">(22)</entry><entry align="center">0.6</entry></row><row><entry align="center"><b>223</b></entry><entry align="center">Cu</entry><entry align="center">Cu(OAc)2</entry><entry align="center">0.3</entry><entry align="center">(108)</entry><entry align="center">0.7</entry><entry align="center">-</entry><entry align="center">15 (Py)</entry><entry align="center">(23)</entry><entry align="center">0.7</entry></row><row><entry align="center"><b>224</b></entry><entry align="center">Ni</entry><entry align="center">Ni(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(109)</entry><entry align="center">0.5</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(24)</entry><entry align="center">0.4</entry></row><row><entry align="center"><b>225</b></entry><entry align="center">Cu</entry><entry align="center">Cu(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(109)</entry><entry align="center">0.5</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(25)</entry><entry align="center">0.4</entry></row><row><entry align="center"><b>226</b></entry><entry align="center">Ni</entry><entry align="center">Ni(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(110)</entry><entry align="center">0.5</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(26)</entry><entry align="center">0.5</entry></row><row><entry align="center"><b>227</b></entry><entry align="center">Co</entry><entry align="center">Co(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(110)</entry><entry align="center">0.5</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(27)</entry><entry align="center">0.4</entry></row><row><entry align="center"><b>228</b></entry><entry align="center">Cu</entry><entry align="center">Cu(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(110)</entry><entry align="center">0.5</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(28)</entry><entry align="center">0.6</entry></row><row><entry align="center"><b>229</b></entry><entry align="center">Ni</entry><entry align="center">Ni(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(111)</entry><entry align="center">0.4</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(29)</entry><entry align="center">0.1</entry></row><row><entry align="center"><b>230</b></entry><entry align="center">Co</entry><entry align="center">Co(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(111)</entry><entry align="center">0.4</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(30)</entry><entry align="center">0.4</entry></row><row><entry align="center"><b>231</b></entry><entry align="center">Cu</entry><entry align="center">Cu(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(111)</entry><entry align="center">0.4</entry><entry align="center">10</entry><entry align="center">10 (ACN)</entry><entry align="center">(31)</entry><entry align="center">0.4</entry></row><row><entry align="center"><b>232</b></entry><entry align="center">Ni</entry><entry align="center">Ni(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(112)</entry><entry align="center">0.4</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(32)</entry><entry align="center">0.2</entry></row><row><entry align="center"><b>233</b></entry><entry align="center">Co</entry><entry align="center">Co(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(112)</entry><entry align="center">0.4</entry><entry align="center">10</entry><entry align="center">-</entry><entry align="center">(33)</entry><entry align="center">0.2</entry></row><row><entry align="center"><b>234</b></entry><entry align="center">Cu</entry><entry align="center">Cu(OAc)2</entry><entry align="center">0.2</entry><entry align="center">(112)</entry><entry align="center">0.4</entry><entry align="center">10</entry><entry align="center">10 (ACN)</entry><entry align="center">(34)</entry><entry align="center">0.4</entry></row><row><entry align="center"><b>235</b></entry><entry align="center">Cu</entry><entry align="center">Cu(OAc)2</entry><entry align="center">0,2</entry><entry align="center">(110) (107)</entry><entry align="center">0,2</entry><entry align="center">-</entry><entry align="center">-</entry><entry align="center">(35)</entry><entry align="center">0,4</entry></row></tbody></tgroup></table></tables><tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="11mm" /><colspec colnum="2" colname="col2" colwidth="19mm" /><colspec colnum="3" colname="col3" colwidth="31mm" /><colspec colnum="4" colname="col4" colwidth="23mm" /><colspec colnum="5" colname="col5" colwidth="38mm" /><thead><row><entry namest="col1" nameend="col5" align="center" valign="top"><b>Table (B2)</b></entry></row><row><entry align="center" valign="top"><b>Ex.</b></entry><entry align="center" valign="top"><b>λ<sub>max</sub> [nm]</b></entry><entry align="center" valign="top"><b>ε (at λ<sub>max</sub>) [l/g/cm]</b></entry><entry align="center" valign="top"><b>MP / DP [°C]</b></entry><entry align="center" valign="top"><b>Compound of formula</b></entry></row></thead><tbody><row><entry align="center"><b>201</b></entry><entry align="center">346</entry><entry align="center">57</entry><entry align="center">281(DP)</entry><entry align="center">(1)</entry></row><row><entry align="center"><b>202</b></entry><entry align="center">370</entry><entry align="center">56</entry><entry align="center">229 (MP)</entry><entry align="center">(2)</entry></row><row><entry align="center"><b>203</b></entry><entry align="center">382</entry><entry align="center">59</entry><entry align="center">285 (DP)</entry><entry align="center">(3)</entry></row><row><entry align="center"><b>204</b></entry><entry align="center">391</entry><entry align="center">64</entry><entry align="center">MP>300 °C</entry><entry align="center">(4)</entry></row><row><entry align="center"><b>205</b></entry><entry align="center">387</entry><entry align="center">63</entry><entry align="center">300 (DP)</entry><entry align="center">(5)</entry></row><row><entry align="center"><b>206</b></entry><entry align="center">363</entry><entry align="center">62</entry><entry align="center">325 (DP)</entry><entry align="center">(6)</entry></row><row><entry align="center"><b>207</b></entry><entry align="center">383</entry><entry align="center">45</entry><entry align="center">275 (DP)</entry><entry align="center">(7)</entry></row><row><entry align="center"><b>208</b></entry><entry align="center">364</entry><entry align="center">46</entry><entry align="center">230 (DP)</entry><entry align="center">(8)</entry></row><row><entry align="center"><b>209</b></entry><entry align="center">380</entry><entry align="center">48</entry><entry align="center">320 (DP)</entry><entry align="center">(9)</entry></row><row><entry align="center"><b>210</b></entry><entry align="center">366</entry><entry align="center">62</entry><entry align="center">187 (MP)</entry><entry align="center">(10)</entry></row><row><entry align="center"><b>211</b></entry><entry align="center">411</entry><entry align="center">64</entry><entry align="center">95 (MP)</entry><entry align="center">(11)</entry></row><row><entry align="center"><b>212</b></entry><entry align="center">392</entry><entry align="center">25</entry><entry align="center">293 (DP)</entry><entry align="center">(12)</entry></row><row><entry align="center"><b>213</b></entry><entry align="center">384</entry><entry align="center">57</entry><entry align="center">185 (MP)</entry><entry align="center">(13)</entry></row><row><entry align="center"><b>214</b></entry><entry align="center">410</entry><entry align="center">75</entry><entry align="center">260 (DP)</entry><entry align="center">(14)</entry></row><row><entry align="center"><b>215</b></entry><entry align="center">402</entry><entry align="center">57</entry><entry align="center">220 (MP)</entry><entry align="center">(15)</entry></row><row><entry align="center"><b>216</b></entry><entry align="center">403</entry><entry align="center">63</entry><entry align="center">263 (DP)</entry><entry align="center">(16)</entry></row><row><entry align="center"><b>217</b></entry><entry align="center">398</entry><entry align="center">54</entry><entry align="center">240 (DP)</entry><entry align="center">(17)</entry></row><row><entry align="center"><b>218</b></entry><entry align="center">413</entry><entry align="center">80</entry><entry align="center">101 (MP)</entry><entry align="center">(18)</entry></row><row><entry align="center"><b>219</b></entry><entry align="center">408</entry><entry align="center">59</entry><entry align="center">200 (DP)</entry><entry align="center">(19)</entry></row><row><entry align="center"><b>220</b></entry><entry align="center">382</entry><entry align="center">60</entry><entry align="center">290 (DP)</entry><entry align="center">(20)</entry></row><row><entry align="center"><b>221</b></entry><entry align="center">413</entry><entry align="center">72</entry><entry align="center">190 (DP)</entry><entry align="center">(21)</entry></row><row><entry align="center"><b>222</b></entry><entry align="center">378</entry><entry align="center">59</entry><entry align="center">235 (MP)</entry><entry align="center">(22)</entry></row><row><entry align="center"><b>223</b></entry><entry align="center">384</entry><entry align="center">74</entry><entry align="center">245 (MP)</entry><entry align="center">(23)</entry></row><row><entry align="center"><b>224</b></entry><entry align="center">448</entry><entry align="center">55</entry><entry align="center">MP>300 °C</entry><entry align="center">(24)</entry></row><row><entry align="center"><b>225</b></entry><entry align="center">413</entry><entry align="center">34</entry><entry align="center">225 (DP)</entry><entry align="center">(25)</entry></row><row><entry align="center"><b>226</b></entry><entry align="center">349</entry><entry align="center">50</entry><entry align="center">MP>300 °C</entry><entry align="center">(26)</entry></row><row><entry align="center"><b>227</b></entry><entry align="center">384</entry><entry align="center">53</entry><entry align="center">260 (DP)</entry><entry align="center">(27)</entry></row><row><entry align="center"><b>228</b></entry><entry align="center">378</entry><entry align="center">68</entry><entry align="center">210 (DP)</entry><entry align="center">(28)</entry></row><row><entry align="center"><b>229</b></entry><entry align="center">397</entry><entry align="center">68</entry><entry align="center">250 (DP)</entry><entry align="center">(29)</entry></row><row><entry align="center"><b>230</b></entry><entry align="center">389</entry><entry align="center">64</entry><entry align="center">220 (MP)</entry><entry align="center">(30)</entry></row><row><entry align="center"><b>231</b></entry><entry align="center">385</entry><entry align="center">73</entry><entry align="center">MP>300 °C</entry><entry align="center">(31)</entry></row><row><entry align="center"><b>232</b></entry><entry align="center">405</entry><entry align="center">36</entry><entry align="center">MP>300 °C</entry><entry align="center">(32)</entry></row><row><entry align="center"><b>233</b></entry><entry align="center">425</entry><entry align="center">26</entry><entry align="center">MP>300 °C</entry><entry align="center">(33)</entry></row><row><entry align="center"><b>234</b></entry><entry align="center">373</entry><entry align="center">53</entry><entry align="center">MP>300 °C</entry><entry align="center">(34)</entry></row><row><entry align="center"><b>235</b></entry><entry align="center">377</entry><entry align="center">66</entry><entry align="center">220 (DP)</entry><entry align="center">(35)</entry></row></tbody></tgroup></table></tables>
Application Example 1
0082The optical and thermal properties of the compounds of formula (I) were studied. The compounds of formula (I) show high absorptions at the desired wavelengths. In addition, the shapes of the absorption spectra, that still remain critical to the disc reflectivity and formation of clean mark edges, are composed of one major band, comprised in a range of from 340 to 500 nm. More precisely, n values of the refractive index were evaluated between 1.0 and 1.9. Light stabilities were found comparable to commercial dyes which are already stabilized with quenchers for the use in optical data recording. Sharp threshold of thermal decomposition within the required temperature range characterizes the compounds of formula (I) which are desirable for the application in optical layers for optical data recording.
Application example 2 Optical layer and optical data recording medium
0083For the optical layer, a 25 nm thick reflection layer of silver was applied to a 1.1 mm thick spiral like pre-grooved polycarbonate disc (made by injection molding, diameter 120 mm, groove depth 28 nm, track width 140 nm, track spacing 320 nm) using sputtering technology. Using the spin-coating process a 2% solution of solution of the compounds of formulae (I) in 2,2,3,3-tetrafluoropropanol was applied onto the reflection layer (recording layer). After drying for 20 min at 75 °C the resulting thickness of recording layer was 80 nm. On the recording layer was applied a 10 nm thick layer of SiON by reactive sputtering as a barrier layer. For protecting the reflective layer, recording layer and barrier-layer, a cover layer/film consisting of polycarbonate (80 µm thickness) is laminated on the surface of the barrier layer using binder. The total thickness of cover layer and binder is set to be 100 µm. The barrier layer, binding layer and cover layer are connected by pressure welding.
0084The testing conditions are the following ones: <ul id="ul0004" list-style="bullet" compact="compact"><li>Numerical aperture (NA) of the optical head: 0.85</li><li>Wavelength of a laser light for recording and reproduction: 405 nm</li><li>Track pitch: 0.32 µm</li></ul>
0085Results of the evaluation tests are summarized in table (C), Pw and CNR were determined for the 8T signal. <tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="38mm" /><colspec colnum="2" colname="col2" colwidth="13mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="23mm" /><thead><row><entry namest="col1" nameend="col4" align="center" valign="top"><b>Table (C)</b></entry></row><row><entry align="center" valign="top"><b>Compound of formula</b></entry><entry align="center" valign="top"><b>Pw</b></entry><entry align="center" valign="top"><b>CNR</b></entry><entry align="center" valign="top"><b>Reflectivity</b></entry></row></thead><tbody><row><entry align="center" /><entry align="center"><b>[mW]</b></entry><entry align="center"><b>[dB]</b></entry><entry align="center"><b>[%]</b></entry></row><row><entry align="center"><b>(1)</b></entry><entry align="center">6</entry><entry align="center">60</entry><entry align="center">14</entry></row></tbody></tgroup></table></tables>
57 sheets
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Every citation, both ways
| Document | Relation | Office | Category | Cited during | Relevant claims |
|---|---|---|---|---|---|
| CN108191793A | Cited by | China | – | Search report | – |
| US11479529B2 | Cited by | United States of America | – | Applicant | – |
| EP0302497A2 | Cites | European Patent Office (EPO) | Y | Search report | 1-19 |
| EP0302497A2 | Cites | European Patent Office (EPO) | Y | Search report | 1-19 |
| FR1396825A | Cites | France | X | Search report | 1,2,4-9 |
| FR1396825A | Cites | France | X | Search report | 1,2,4-9 |
| CN1510014A | Cites | China | X | Search report | 1,2,4-9 |
| EP1577282A2 | Cites | European Patent Office (EPO) | A | Search report | 10,11 |
| EP1577282A2 | Cites | European Patent Office (EPO) | A | Search report | 10,11 |
| JP2004034645A | Cites | Japan | DY | Search report | 1-19 |
| JP2004034645A | Cites | Japan | DY | Search report | 1-19 |
| A.TAKEUCHI ET AL.: "ESR Studies on Salicylaldehyde Schiff Base Complexes of Copper(II)", BULL.CHEM.SOC.JPN., vol. 58, 1985, pages 2987 - 2989, XP002437365 | Non-patent | – | – | Search report | – |
| TURWATKAR S L ET AL: "SYNTHESIS AND CHARACTERISATION OF NOVEL MERCURIC COMPLEXES", ASIAN JOURNAL OF CHEMISTRY, CHEMIC PUBLISHING, SAHIBADAD, IN, vol. 8, no. 4, 1996, pages 676 - 680, XP009085025, ISSN: 0970-7077 | Non-patent | – | – | Search report | – |
| HIGSON B M ET AL: "STEREOCHEMISTRY OF BIS (SALICYLALDIMINATO)METAL (II) COMPOUNDS. PART I BIS ÄN-(2,6-DIALKYLPHENYL) SALICYLIDENEIMINATOÜNICKEL(II) COMPOUNDS AND FIVE-AND SIX-CO-ORDINATE PYRIDINE AND PICOLINE COMPLEXES", JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS, CHEMICAL SOCIETY. LETCHWORTH, GB, vol. 16, 1974, pages 1690 - 1699, XP009085061, ISSN: 1472-7773 | Non-patent | – | – | Search report | – |
| CUIYING LIU ET AL: "SYNTHESIS AND ANTIBACTERIAL ACTIVITIES OF 5-NITRO-N(2-HYDROXYETHYL)SA LICYLALDIMINE WITH COPPER(II)", HUAXI YAOXUE ZAZHI - WEST CHINA JOURNAL OF PHARMACEUTICAL SCIENCES, ZHONGGUO YAOXUEHUI, SICHUAN FENHUI, CHENGDU, CN, vol. 11, no. 2, 1996, pages 69 - 71, XP009085027, ISSN: 1006-0103 | Non-patent | – | – | Search report | – |
| KASUMOV ET AL.: "Preparation and Redox Properties of Pd(II) complexes", KOORDINATSIONNAYA KHIMIYA, vol. 15, no. 10, 1989, pages 1404 - 1407, XP009085032 | Non-patent | – | – | Search report | – |
| R.H.HOLM: "Studies on Nickel(II) Complexes", JACS, vol. 83, no. 23, 1961, pages 4683 - 4690, XP002437366 | Non-patent | – | – | Search report | – |
| RAMANATHAN J D ET AL: "BIOLOGICAL ACTIVITY OF SOME 2-AMINO 4,5,6,7-TETRAHYDRO BENZO(B)-THIOPHENES AND THEIR DERIVATIVES", JOURNAL OF THE INDIAN CHEMICAL SOCIETY, INDUSTRIAL AND NEWS EDITION, INDIAN CHEMICAL SOCIETY, CALCUTTA, IN, vol. 55, August 1978 (1978-08-01), pages 822 - 825, XP009084980, ISSN: 0375-9008 | Non-patent | – | – | Search report | – |
| S.MUKHOPADHYAY ET AL.: "Equilibrium Studies in Solution involving Nickel(II) Complexes of flexidentate Schiff Base Ligands", INORG.CHEM., vol. 42, 2003, pages 8439 - 8445, XP002437367 | Non-patent | – | – | Search report | – |
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| 06291773 | European Patent Office (EPO) | A | |
| EP20060291773 | – | – | – |
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Titles3
- German
- Nitro-Schiffsche Base Metallkomplexfarbstoffe und deren Verwendung in Schichten zur optischen Datenspeicherung
- English
- Nitro schiff base metal complex dyes and their use in optical layers for optical data recording
- French
- Complexes metalliques a base de Schiff et matériaux optiques d'enregistrement les contenant
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