EP1599548A1

EP1599548A1 - Metal complexes as light-absorbing compounds in the information layer of optical data carriers

Info

Publication number: EP1599548A1
Application number: EP04707150A
Authority: EP
Inventors: Horst Berneth; Friedrich-Karl Bruder; Rainer Hagen; Karin HASSENRÜCK; Serguei Kostromine; Christa-Maria KRÜGER; Timo Meyer-Friedrichsen; Rafael Oser; Josef-Walter Stawitz
Original assignee: Lanxess Deutschland GmbH
Current assignee: Lanxess Deutschland GmbH
Priority date: 2003-02-13
Filing date: 2004-01-31
Publication date: 2005-11-30
Also published as: CN1774481A; US20060280894A1; WO2004072184A1; JP2006519889A; TW200501141A; DE10305924A1

Abstract

The invention relates to novel metal complexes for optical data carriers, whereby the latter preferably a transparent substrate which is, optionally, already covered with one or several reflective layers. A light-inscriptible information layer is disposed on the surface thereof, in addition to, optionally, one or several reflective layers and, optionally, a protective layer or another substrate or a covering layer which is inscriptible or readable with blue, red or infrared light, preferably laser light. The information layer contains a light-absorbing compound and, optionally, a binding agent. The invention is characterised in that the at least said metal complex is used as a light-absorbing compound.

Description

Metal complexes as light-absorbing compounds in the information layer of optical data carriers

The invention relates to metal complexes, a process for their preparation, the azo compounds functioning as ligands of the metal complexes and their production, the coupling components on which the azo compounds are based and their production, and optical data memories which contain the metal complexes in their information layer, and the application of the dyes mentioned above a polymer substrate, in particular polycarbonate, by spin coating or vapor deposition.

The write-once optical data carriers using special light-absorbing substances or their mixtures are particularly suitable for use in high-density writable optical data memories which work with blue laser diodes, in particular GaN or SHG laser diodes (360 - 460 nm) and / or for the Use with DVD-R (DVD-R, DVD + R) or CD-R discs that work with red (635 - 660 nm) or infrared (780 - 830 nm) laser diodes.

The once writable Compaet Disk (CD-R, 780 nm) has been experiencing an enormous amount recently

Volume growth and represents the technically established system.

The next generation of optical data storage media - the DVD - is currently being launched on the market. The storage density can be increased by using shorter-wave laser radiation (635 to 660 nm) and a higher numerical aperture NA. The recordable format in this case is the DVD-R.

Today, optical data storage formats using blue laser diodes (based on GaN, JP 08191171 or Second Harmonie Generation SHG JP 09050629) (360 nm to 460 nm) with high laser power are being developed. Writable optical data storage devices will therefore also be used in this generation. The storage density that can be achieved depends on the focus of the laser spot in the information level. The spot size scales with the laser wavelength λ / NA. NA is the numerical aperture of the objective lens used. In order to obtain the highest possible storage density, the aim should be to use the smallest possible wavelength λ. 390 nm are currently possible on the basis of semiconductor laser diodes.

The patent literature describes dye-based writable optical data storage devices which are equally suitable for CD-R and DVD-R (DVD-R, DVD + R) systems

(JP-A 11 043 481 and JP-A 10 181 206). It is for a high reflectivity and a high

Modulation height of the readout signal, as well as for sufficient sensitivity when use the fact that the IR wavelength 780 nm of the CD-R lies at the foot of the long-wave flank of the absorption peak of the dye, the red wavelength 635 nm and 650 nm of the DVD-R (DVD-R, DVD + R ) lies at the foot of the short-wave edge of the absorption peak of the dye. This concept is described in JP-A 02 557 335, JP-A 10 058 828, JP-A 06 336086, JP-A 02 865 955, WO-A 09 917284 and US-A 5 266 699 in the 450 nm range

Working wavelength extended on the short-wave flank and the red and IR range on the long-wave flank of the absorption peak.

In addition to the optical properties mentioned above, the writable information layer made of light-absorbing organic substances must have a morphology which is as amorphous as possible in order to keep the noise signal as small as possible when writing or reading. For this purpose, it is particularly preferred that when the substances are applied by spin coating from a solution, by vapor deposition and / or sublimation, subsequent crystallization of the light-absorbing substances with metallic or dielectric layers in vacuum is prevented.

The amorphous layer of light-absorbing substances should preferably have a high heat resistance, since otherwise other layers of organic or inorganic material, which are applied to the highly absorbing information layer by sputtering or vapor deposition, form blurred interfaces via diffusion and thus adversely affect the reflectivity. In addition, a light-absorbing substance with too low heat resistance at the interface to a polymer carrier can diffuse in it and in turn adversely affect the reflectivity.

An excessively high vapor pressure of a light-absorbing substance can sublimate the above-mentioned sputtering or vapor deposition of further layers in a high vacuum and thus reduce the desired layer thickness. This in turn leads to a negative influence on the reflectivity.

The object of the invention is therefore to provide suitable compounds that are high

Meet requirements (such as light stability, favorable signal-to-noise ratio, damage-free application to the substrate material, etc.) for use in the information layer in a write-once optical data carrier, in particular for high-density recordable optical data storage formats in a laser wavelength range from 340 to 680 nm ,

It has surprisingly been found that highly absorbent compounds from the group of special metal complexes can meet the above-mentioned requirement profile particularly well.

The invention therefore relates to metal complexes which have at least one ligand of the formula (ϊ)

embedded image in which

X ^{1 represents} O, S, NR ¹ or CH,

A together with X ¹ and N represents a five- or six-membered aromatic or quasi-aromatic heterocyclic ring which contains 1 to 4 heteroatoms and / or benzylated or naphthanellated and / or can be substituted by nonionic radicals,

R ¹ for hydrogen, optionally substituted C 1 -C ₂ alkyl, optionally substituted

C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C _{! 2} alkenyl or optionally substituted C ₇ -Cι ₂ aralkyl,

R ² and R ³ are independently hydrogen, optionally substituted Cι-Cι ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ ₅ -Cι ₂ - ^■ alkenyl, optionally substituted C ₂ -Cι ₂ alkynyl, optionally substituted C ₇ -C ₂ aralkyl, optionally substituted C _o -Cio aryl or a five- or six-membered heterocyclic ring or

NR ² R ³ together with the nitrogen atom for a five- to seven-membered heterocyclic

Ring which may contain further heteroatoms and / or which may be substituted by nonionic radicals,

R ⁴ and R ⁵ independently of one another represent hydrogen, halogen, optionally substituted C ₁ -C ₆ -alkyl, optionally substituted C ₁ -C ₆ alkoxy, optionally substituted CC ₆ alkylthio or

R ² ; R ⁴ and R ³ ; R ⁵ independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,

Y stands for SCVY ¹ or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ , Y ² and Y ³ independently of one another for optionally substituted C Ci ₂ alkyl, optionally substituted Gβ-Cio-Arvl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical, -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ stand or Y ² and Y ³ stand together for a bridge,

R ⁶ and R ⁷ independently of one another are optionally substituted -C ^ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -Cι ₂ alkenyl, optionally substituted C ₂ -Cι ₂ alkynyl, optionally substituted C ₇ -Cι ₂ aralkyl, optionally substituted Cβ-Cio-aryl or a five- or six-membered heterocyclic ring or

NR ⁶ R ⁷ together with the nitrogen atom for a five- to seven-membered heterocyclic

or metal complexes which have at least one ligand of the formula (LI)

wherein

X ^{2 represents} N or CH

and the other radicals have the meaning given above.

In a preferred embodiment, the metal complexes are present as 1: 1 or 1: 2 metalhazo complexes.

Those metal complexes which have two identical or different ligands of the

Contain formula (I).

Those metal complexes which contain two identical or different ligands of the formula (LI) are clearly preferred.

Preferred metal complexes are those which are characterized in that they have the formula (Ia) [(,)] 2+

M (Ia)

correspond in which the two ligands of the formula (I) independently of one another have the meaning given above and

M stands for a metal.

Also preferred are those metal complexes which are characterized in that they are the

Formula (Ib)

[0 »] (Ib)

M ³⁺ arr

2

M stands for a metal and

An ^"stands for an anion.

Also preferred are statistical mixtures of metal complexes which are characterized in that they contain two different ligands of the formula I.

Preferred metals are divalent metals, transition metals or rare earths, in particular Mg, Ca, Sr, Ba, Cu, Ni, Co, Fe, Zn, Pd, Pt, Ru, Th, Os, Sm, Eu. The metals Pd, Fe, Zn, Cu, Ni and Co. are preferred. Ni and Zn are particularly preferred.

Also preferred metals are trivalent metals, transition metals or rare earths. In this case, the excess third charge of the metal is compensated for by an anion. B, Al, Ga, In, V, Co, Cr, Fe, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb are particularly suitable. B, Al, Co. are preferred. Co. is particularly preferred.

Nonionic radicals are, for example, halogen, alkyl, alkenyl, aralkyl, aryl, alkoxy, alkylthio, hydroxy, amino, alkylamino, dialkylamino, cyano, iro, alkoxycarbonyl, alkylamino or dialall <ylaminocarbonyl, -C (= NH) -0- Alkyl, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl. Halogen, in particular Cl or F, nitro, cyano, hydroxy, CO-NH 2, CO-O-alkyl or alkoxy, come in as possible substituents of the alkyl, alkoxy, alkylthio, cycloalkyl, aralkyl, aryl or hererocyclic radicals Question. The alkyl radicals can be straight-chain or branched and they can be partially or perhalogenated. Examples of substituted alkyl radicals are trifluoromethyl, chloroethyl, cyanoethyl, methoxyethyl. Examples of branched alkyl radicals are

Isopropyl, tert-butyl, 2-butyl, neopentyl.

Preferred optionally substituted C 1 -C 4 -alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl, octyl, decyl, dodecyl , perfluorinated methyl, perfluorinated ethyl, 3,3,3-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, perfluorobutyl, cyanoethyl, methoxyethyl.

Examples of preferred aralkyl include benzyl, phenethyl or phenylpropyl.

Preferred heterocyclic radicals are furyl, thienyl, thiazolyl, benzthiazolyl, oxazolyl, benzoxazolyl, imidazolyl, benzimidazolyl, pyridyl, pyrimidyl, pyrazinyl, quinolyl, which can be substituted by methyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl.

Anions An ^" include all monovalent anions or an equivalent of a multivalent

Anion or an equivalent of an oligomeric or polymeric anion in question. They are preferably colorless anions. Suitable anions are, for example, chloride, bromide, iodide, nitrate, tetrafluoroborate, perchlorate, hexafluorosilicate, hexafluorophosphate, methosulfate, ethosulfate, Q- to Cio-alkanesulfonate, C to Cio-perfluoroalkanesulfonate, optionally by chlorine, hydroxy, - to C ₄ - alkoxy substituted Ci to Cio alkanoate, optionally by nitro, cyano, hydroxy, - bis

C ₂₅ -alkyl, perfluoro-Cj- to C -AlkyL C_- to C ₄ -alkoxycarbonyl or chlorine-substituted benzene or naphthalene or biphenyl sulfonate, optionally with nitro, cyano, hydroxy, C to C ₄ - alkyl, Ci- to C ₄ - Alkoxy, C to C ₄ alkoxycarbonyl or chlorine substituted benzene or naphthalene or biphenyl disulfonate, optionally by nitro, cyano, - to C ₄ alkyl, Ci to C ₄ alkoxy, - to alkoxycarbonyl, benzoyl, chlorobenzoyl or toluoyl substituted

Benzoate, the anion of naphthalenedicarboxylic acid, diphenyl ether disulfonate, tetraphenyl borate, cyanotriphenyl borate, tetra-Ci to C ₂ o-alkoxyborate, tetraphenoxyborate, 7,8- or 7,9-dicarbanidoundecaborate (l-) or (2-), which may be given to the B and / or C atoms are substituted by one or two C 1 to C ₂ alkyl or phenyl groups, dodecahydro dicarbadodecaborate (2-) or BC to C ₂ alkyl C-phenyl dodecahydro dicarbadodecaborate ( l)

Polystyrene sulfonate, poly (meth) acrylate, polyallylsulfonate. Bromide, iodide, tetrafluoroborate, perchlorate, hexafluorophosphate, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, toluenesulfonate, dodecylbenzenesulfonate, tetradecanesulfonate, polystyrene sulfonate are preferred.

Can continue as anions An ^"all monovalent anions or one equivalent of a polyvalent anion of a dye can be used. Preferably, the anionic dye ^to" an absorption spectrum similar to the cationic azo metal salt. Suitable examples are anionic azo dyes, anthraquinone dyes, porphyrins, phthalocyanines, subphthalocyanines, cyanines, merocyanines, rhodamines, metal complexes and oxonols.

The metal complexes of the formula (Ia) are presumably in the form of the formula (ET)

wherein M and the residues of the respective azo ligands have the meaning given above independently of one another. In the context of this application it is assumed that formulas (H) and (Ia) characterize the same compounds.

Metal complexes of ligands of the formula (I), in particular (Ia) or (Ib), in which

the ring A of the formula (TJJ)

for benzthiazol-2-yl, benzoxazol-2-yl, benzimidazol-2-yl, thiazol-2-yl, thiazol-4-yl, unidazol-2-yl, pyrazol-5-yl, l, 3,4-thiadiazole -2-yl, l, 2,4-thiadiazol-5-yl, 1,2,4-thiadiazol-3-yl, l, 3,4-oxadiazol-2-yl, l, 3,4-triazol-2 -yl, 2-pyridyl, 2-quinolyl, 3-pyridazinyl, 2- Pyrimidyl, l, 3,5-triazin-2-yl or 2-pyrazinyl, which is substituted by Q to C ₆ alkyl, Ci to C ₆ alkoxy, fluorine, chlorine, bromine, iodine, cyano, -C ( = NH) -0-C to C ₆ -alkyl, nitro, C to C ₆ -alkoxycarbonyl, - to C ₆ -alkylthio, Ci- to C ₆ -acylamino, formyl, C ₂ -C ₆ -alkanoyl, C ₆ - to o-aryl, C ₆ - to Cι ₀ aryloxy, C ₆ - to Cι ₀ arylcarbonylamino, mono- or di- to C ₆ alkylamino, N - to C ₆ alkyl-NC ₆ - to Cio- Arylamino, pyrrolidino, morpholino,

Piperazino or Piperidino can be substituted,

in which

X ^{1 represents} O, S, NR ¹ or CH.

R ^{1 represents} hydrogen, Q to C ₄ alkyl, allyl or C ₇ to C ₉ aralkyl,

Y stands for SOz-Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ ,

Y ² and Y ³ independently of one another for methyl, ethyl, trifluoromethyl, 2,2,2-trifluoroethyl,

2,2-difluoroethyl, phenyl, tolyl, -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ or Y ² and Y ³ together represent a ~ (CH ₂ ) ₄ -, - (CH ₂ ) ₅ - or -CH ₂ -CH = CH-CH ₂ bridge,

R ⁶ and R ⁷ independently of one another, optionally by fluorine, chlorine, hydroxy, methoxy,

CC ₈ -alkyl substituted by ethoxy or cyano, Cs-Cg-cycloalkyl, allyl, optionally substituted by chlorine, methyl or methoxy C ₇ -C ₉ -aryl, optionally substituted by phenyl substituted by fluorine, chlorine, hydroxy, methoxy, ethoxy, nitro or cyano or pyridyl or

NR ⁶ R ^{7 represents} pyrrolidino, piperidino or morpholino,

and all other radicals have the meaning given above.

Metal complexes of ligands of the formula (I), in particular (Ia), are very particularly preferred,

wherein

the ring A of the formula (DT)

for benzthiazol-2-yl, which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, ethoxy, cyano or nitro, benzimidazol-2-yl, which can be substituted by up to three identical or different radicals the series chlorine, methyl, methoxy, ethoxy, cyano or nitro can be substituted, thiazol-2-yl, which is replaced by up to two identical or different radicals from the series chlorine, fluorine, methyl, trifluoromethyl,

Methoxy, phenyl, cyano, nitro, methoxycarbonyl, methanesulfonyl, formyl or a bivalent radical of the formula - (CH ₂ ) ₄ - can be substituted, thiazol-4-yl, which can be substituted by up to two identical or different chlorine radicals , Fluorine, methoxy, methylthio, phenyl or cyano can be substituted, imidazol-2-yl, which can be substituted by up to two identical or different radicals from the series fluorine, chlorine, methyl, trifluoromethyl,

Methoxy, phenyl, cyano, nitro, CH ₃ 0- (C = NH) -, methoxycarbonyl or ethoxycarbonyl can be substituted, pyrazol-5-yl, which is replaced by up to two identical or different radicals from the series chlorine, methyl, methoxy, Phenyl, cyano or nitro can be substituted, l, 3,4-thiadiazol-2-yl, which by chlorine, bromine, methoxy, phenoxy, methanesulfonyl, methylthio, ethylthio, dimethylamino, diethylamino, di- (iso) propylamino, N -methyl-N-

Cyanethylamino, N, N-biscyanethylamino, N-methyl-N-hydroxyethylamino, N-methyl-N-benzylamino, N-methyl-N-phβnylamino, anilino, pyrrolidino, piperidino or morpholino can be substituted, l, 2,4-thiadiazole -5-yl, which can be substituted by chlorine, methyl, methoxy, phenoxy, methylthio, methanesulfonyl, phenyl, dimethylamino or anilino, l, 2,4-thiadiazol-3-yl, which can be substituted by methyl or phenyl, 1 , 3,4-triazole

2-yl, which can be substituted by methyl or phenyl, 2-pyridyl, which can be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 2-quinolyl, which can be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or Nitro can be substituted, 2-pyrimidyl. which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 1,3,5-

Triazin-2-yl or 2-pyrazinyl,

in which

X ^{1 represents} O, S, NR ¹ or CH,

R ^{1 represents} hydrogen, methyl, ethyl, propyl, butyl, allyl, benzyl, phenethyl or phenylpropyl,

R ² and R ³ independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, hydroxyethyl, cyanoethyl, cyclopentyl, cyclohexyl, allyl, benzyl, phenethyl, phenylpropyl, phenyl, tolyl, chlorophenyl or anisyl or NR ² R ^{3 represents} pyrrolidino, piperidino or morpholino,

R ^{4 represents} hydrogen, chlorine, methyl, methoxy or methylthio,

R ^{5 represents} hydrogen or methyl or

R ² ; R ⁴ and R ³ ; R ⁵ independently of one another are - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -C (CH ₃ ) 2-CH ₂ -CH (CH ₃ ) - or -0 (CH ₂ ) ₂ -,

Y stands for SO ₂ -Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -NH-R ⁶ or -NR ⁶ R ⁷ ,

Y ² and Y ^{3 are the} same and represent methyl, ethyl, -OR ⁶ , -NH-R ⁶ or -NR ⁶ R ⁷ or Y ² and

Y ³ together represent a - (CH ₂ ) bridge, or

Y ^{2 represents} phenyl and

Y ^{3 represents} -OR ⁶ , -NH-R ⁶ or -NÄ ⁷ ,

R ⁶ and R ⁷ independently of one another for methyl, ethyl, propyl, butyl, 2,2,2-trifluoroethyl, 2,2-

Difluoroethyl, 2,2,3,3-tetrafluoropropyl, 1H, 1H-heptafluorobutyl, 1H, 1H, 4H-hexafluorobutyl, cyclohexyl, allyl, benzyl or phenyl or

E TR. ^{7 represents} pyrrolidino, piperidino or morpholino,

M stands for nickel, zinc, copper, cobalt, iron or palladium.

Metal complexes of ligands of the formula (I), in particular (Ib), are also very particularly preferred.

wherein

M represents boron, aluminum or cobalt,

An ^"stands for iodide, nitrate, tetrafluoroborate, perchlorate, hexafluorophosphate, methanesulfonate, trifluoromethanesulfonate or the anion or an equivalent of an anion of a rhodamine, oxonol or azo metal complex dye

and the other radicals have the meaning given above.

Suitable rhodamine dyes are those of the formula (C)

embedded image in which

R ¹⁰¹ and R ¹⁰³ independently of one another represent hydrogen, methyl or ethyl,

R and R independently of one another represent a phenyl, naphthyl, benzthiazolyl or benzoxazolyl radical which is substituted by sulfo or carboxy and which may be substituted by chlorine, hydroxyl, methyl, methoxy or methylthio,

R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁸ and R ^{109 are} independently hydrogen, methyl or methoxy or

_R ιoι. _R ιo ⁵ _{} R} ιo ² . _R ι <κ _R ιo ³ . _R ιos _{md R} ιo4. _R ιo? _{independently of} one another are - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -C (CH ₃ ) ₂ -CH ₂ -CH (CH ₃ ) - or -0 (CH ₂ ) ₂ - and

R ^] 107 represents hydrogen or sulfo.

Suitable oxonol dyes are those of the formula (Cϊ)

embedded image in which

the rings B and C represent a five- or six-membered, carbocyclic or heterocyclic ring.

In formula (CI), B and C are preferably the same. Ring B together with the two carbon atoms and the oxygen atom preferably represent a radical of the formulas

and the ring C together with the two carbon atoms and the oxygen atom for a remainder of the formulas

O -Γ Y R.111

embedded image in which

R ¹ * ¹ and R ¹¹² independently of one another represent hydrogen or methyl,

R ¹ 113 represents methyl or trifluoromethyl,

R 114 represents cyano, methoxycarbonyl or ethoxycarbonyl, R 115 represents phenyl, chlorophenyl or tolyl.

Suitable azo metal complex dyes are those of the formula (CH)

embedded image in which

Y and Y independently of one another represent -O- or -COO-,

M-101 stands for a divalent or trivalent metal and

the benzene rings can be benzanellated and / or substituted by nonionic radicals.

Nonionic residues are defined above.

M preferably represents Ni, Co, Cr, Fe, Cu.

Such metal complexes of ligands of the formula (ϊ) are particularly preferred, in particular

(Ia)

embedded image in which

the ring A of the formula (DJ)

for benzothiazol-2-yl, chlorobenzthiazol-2-yl, methylbenzthiazol-2-yl, methoxybenzthiazol-2-yl or nitrobenzthiazol-2-yl, benzimidazol-2-yl, thiazol-2-yl, phenylthiazol-2-yl, cyanothiazol -2-yl, nitrothiazol-2-yl, 5-fluoro-4-trifluoromethylthiazol-2-yl, 5-phenyl-4-trifluoromethylthiazol-2-yl, 2-methylthio-5-cyano-thiazol-4-yl, imidazole -2-yl, 4,5- Diphenylimidazol-2-yl, 4,5-dicyanoimidazol-2-yl, 4,5-bis-methoxycarbonylimidazol-2-yl or 4,5-bis-ethoxycarbonylimidazol-2-yl, pyrazol-5-yl, 1,3, 4-thiadiazol-2-yl, 5-phenoxy-1, 3, 4-thiadiazol-2-yl, 5-methylthio-1, 3, 4-thiadiazol-2-yl, 5-dimethylamino-1, 3, 4- thia-diazol-2-yl, 5-diethylamino-l, 3,4-thiadiazol-2-yl, 5-di- (iso) -propylamino-l, 3,4-thiadiazol-2-yl, 5-N- Methyl-N-cyanoethylamino-l, 3,4-thiadiazol-2-yl, 5-pyrrolidino-l, 3,4-thiadiazol-

2-yl, 5-phenyl-l, 3,4-thiadiazol-2-yl, 5-methyl-l, 3,4-thiadiazol, l, 2,4-thiadiazol-5-yl, 3-methylthio-l, 2,4-thiadiazol-5-yl, 3-methanesulfonyl-l, 2,4-thiadiazol-5-yl, 3-phenyl-l, 2,4-thiadiazol-5-yl, 5-methyl-l, 2, 4-thiadiazol-3-yl, l, 3,4-triazol-2-yl, 2-pyridyl, 2-quinolyl, 2-pyrimidyl, 4-cyano-2-pyrimidyl, 4,6-dicyano-2-pyrimidyl, l, 3,5-triazin-2-yl or 2-pyrazinyl,

in which

X ¹ for O, S, NR ^! or CH stands,

R ^{1 represents} hydrogen, methyl, ethyl or benzyl,

R ² and R ³ independently of one another represent methyl, ethyl, cyanoethyl, cyclohexyl, benzyl or phenyl or

NR ² R ^{3 represents} pyrrolidino, piperidino or morpholino,

R ^{4 represents} hydrogen, methyl or methoxy,

R ^{5 represents} hydrogen or

R ² ; R ^{4 represents} - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ -,

Y stands for SO ₂ -Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -NH-R ⁶ or -NRV,

Y ² and Y ^{3 are the} same and stand for -OR ⁶ ,

R ⁶ and R ⁷ independently of one another are methyl, ethyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl,

2,2,3,3-tetrafluoropropyl, benzyl or phenyl are or

NR ⁶ R ^{7 represents} pyrrolidino, piperidino or morpholino,

M stands for nickel, zinc, copper or cobalt. Such metal complexes of ligands of the formula (I), in particular (Ib), are also extremely preferred.

embedded image in which

M stands for cobalt,

An ^" for iodide, nitrate, tetrafluoroborate, perchlorate, hexafluorophosphate or the anion of the formula

stands

and the other radicals have the meaning given above.

The ring A of the formula (IH)

preferably stands for 4,5-dicyanoimidazol-2-yl, l-methyl-4,5-dicyanoimidazol-2-yl, l-ethyl-4,5-dicyanoimidazol-2-yl, l-benzyl-4,5-dicyanoimidazole -2-yl, l- (2,2,2-trifluoroethyl) -4,5-dicyanoimidazol-2-yl, 3-phenyl-l, 2,4-thiadiazole, 3-pyridyl-l, 2,4 -thiadiazole, 3-methanesulfonyl-l, 2,4-thiadiazole, 5-dimethylamino-l, 3,4-thiadiazole, 5-diisopropylamino-l, 3,4-thiadiazole, 5-pyrrolidino-

1,3,4-thiadiazole, 5-phenyl-l, 3,4-thiadiazol-2-yl, 5-methyl-l, 3,4-thiadiazole, 2-pyridyl, 2-pyrimidyl, 4-cyano2-pyrimidyl.

The metal complexes according to the invention come in particular as powder or granules or as

Solution with a solids content of at least 2 wt .-% in the trade. The granulate form is preferred, in particular granules with an average particle size of 50 μm to 10 mm, in particular especially 100 to 800 μm. Such granules can be produced, for example, by spray drying. The granules are particularly characterized by their low dust level.

The metal complexes according to the invention are notable for good solubility. They are readily soluble in non-fluorinated alcohols. Such alcohols are, for example, those with 3 to 6 carbon atoms, preferably propanol, butanol, pentanol, hexanol, diacetone alcohol or else

Mixtures of these alcohols, such as. B. propanol / diacetone alcohol, butanol / diacetone alcohol, butanol hexanol. Preferred mixing ratios for the listed mixtures are, for example, 80:20 to 99: 1, preferably 90:10 to 98: 2.

The concentrated solutions are also preferred. They are at least 1% by weight, preferably at least 2% by weight, particularly preferably at least 5% by weight, of the metal complexes according to the invention, in particular those of the formulas (Ia), (Ib) or (H). 2,2,3,3-tetafluoropropanol, propanol, butanol, pentanol, hexanol, diacetone alcohol, dibutyl ether, heptanone or mixtures thereof are preferably used as solvents. 2,2,3,3-Tetrafluoropropanol is particularly preferred. Butanol is also particularly preferred. Butanol / diacetone alcohol in a mixing ratio of 90:10 to 98: 2 is also particularly preferred.

The invention further relates to a process for the preparation of the metal complexes of the formulas (Ia) and (Ib) according to the invention, which is characterized in that a metal salt with an azo compound of the formula (Ic)

wherein

X ^{1 represents} O, S, NR ¹ or CH,

together with X ¹ and N represents a five- or six-membered aromatic or quasi-aromatic heterocyclic ring which contains 1 to 4 heteroatoms and / or benzylated or naphthanellated and / or can be substituted by nonionic radicals, R ¹ for hydrogen, optionally substituted -Cπ-alkyl, optionally substituted

C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl or optionally substituted C ₇ -C ₂ aralkyl,

R ² and R ³ independently of one another for hydrogen, optionally substituted -Cπ-alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -Cι ₂ -

Alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ -

C ₂ aralkyl, optionally substituted Cβ-cio-aryl or a five- or six-membered heterocyclic ring or

NR ² R ³ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,

R ⁴ and R ^{5 are} independently hydrogen, halogen, optionally substituted Cι-C ₆ - alkyl, optionally substituted _Cι-C6 alkoxy optionally substituted Cι-C, ₆ - alkylthio or

Y stands for SOz-Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ ,

Y ² and Y ³ independently of one another for optionally substituted C 1 -C ₂ alkyl, optionally substituted C 6 -C 10 aryl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical, -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ stand or Y ² and Y ³ together stand for a bridge,

R ⁶ and R ⁷ independently of one another are optionally substituted -C ^ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -Cι ₂ alkenyl, optionally substituted C ₂ -Cι ₂ alkynyl, optionally substituted C ₇ -C ₂ aralkyl, optionally substituted C ₆ -C ₀ aryl or a five- or six-membered heterocyclic ring or

NR ^ ⁷ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or which may be substituted by nonionic radicals, implements.

Two or more different azo compounds of the formula (Ic) can also be used in this process according to the invention. A statistical mixture of metal complexes is then obtained, consisting of those complexes which contain two identical ligands of the formula (ϊ) and those complexes which contain two different ligands of the formula (I).

These mixtures are also the subject of the invention.

The production of metal complexes and the metal complexes themselves are also meant quite analogously if a mixture of azo compounds of the formulas Ic is used in their production.

The reaction according to the invention is generally carried out in a solvent or solvent mixture, if appropriate in the presence of basic substances, at room temperature to the boiling point of the solvent, for example at 20-100 ° C., preferably at 20-50 ° C. The metal complexes either precipitate directly and can be isolated by filtration or they are precipitated, for example, by adding water, possibly with partial or complete removal of the solvent beforehand, and isolated by filtration. It is also possible to carry out the reaction directly in the solvent to give the concentrated solutions mentioned above.

Metal salts include, for example, the chlorides, bromides, sulfates, hydrogen sulfates, phosphates, hydrogen phosphates, dihydrogen phosphates, hydroxides, oxides, carbonates, hydrogen carbonates, salts of carboxylic acids such as formates, acetates, propionates, benzoates, salts of

To understand sulfonic acids such as methanesulfonates, trifluoromethanesulfonates or benzenesulfonates of the corresponding metals. Metal salts are also to be understood as meaning complexes with ligands other than those of the formulas (T), in particular complexes of acetylacetone and acetoacetic acid esters. Possible metal salts are, for example: nickel acetate, cobalt acetate, copper acetate, nickel chloride, nickel sulfate, cobalt chloride, copper chloride, copper sulfate,

Nickel hydroxide, nickel oxide, nickel acetylacetonate, cobalt hydroxide, basic copper carbonate, barium chloride, iron sulfate, palladium acetate, palladium chloride and their variants containing water of crystallization.

As basic substances come into question alkali acetates such as. B. sodium acetate, potassium acetate, alkali hydrogen carbonates, carbonates or hydroxides such as sodium hydrogen carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, or amines such as ammonia, dimethylamine, triethylamine, diethanolamine. Such basic substances are particularly advantageous when metal salts of strong acids such as metal chlorides or sulfates are used. Suitable solvents are water, alcohols such as methanol, ethanol, propanol, butanol, 2,2,3,3-tetrafluoropanol, ethers such as dibutyl ether, dioxane or tetrahydrofuran, aprotic solvents such as dimethylformamide, N-methylpyrrolidone, acetonitrile, nitromethane, dimethyl sulfoxide , Methanol, ethanol and 2,2,3,3-tetrafluoropropanol are preferred.

The salt-like metal complexes of the formula (Ib) can also be prepared by

Oxidation of metal complexes of the formula (Ia). It can also be carried out by reacting azo dyes of the formula (Ic) with salts of divalent metals in the presence of an oxidizing agent.

Suitable oxidizing agents are, for example, nitric acid, nitrous acid, hydrogen peroxide, Caro's acid, alkali peroxodisulfates, alkali perborates, air, oxygen. Are preferred

Nitric acid and air.

The conditions of the reaction are as given above.

The azo compounds of the formula (Ic) required for the preparation of the metal complexes according to the invention are also the subject of this invention. Some of them are known from EP-A 0 040 171.

The invention therefore also relates to azo compounds of the formula (Ic)

embedded image in which

X ^{1 represents} O, S, NR ¹ or CH,

R ^{1 represents} hydrogen, optionally substituted -Cπ-alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -Cι ₂ alkenyl or optionally substituted C ₇ -Cι ₂ aralkyl, R ² and R ³ independently of one another for hydrogen, optionally substituted CC ₁₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C _{] 2} -

Alkenyl, optionally substituted C ₂ -C ₁₂ alkynyl, optionally substituted C ₇ -

Ci ₂ aralkyl, optionally substituted C ₆ -C ₁₀ aryl or a five- or six-membered heterocyclic ring or

R ⁴ and R ^{5 are} independently hydrogen, halogen, optionally substituted Cι-C ₆ - alkyl, optionally substituted Cι-C ₆ -alkoxy, unsubstituted or substituted Cι-C ₆ -

Alkylthio stand or

Y stands for SOz-Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR'TR ⁷ ,

Y ² and Y ³ independently represent optionally substituted _Cι-C12 alkyl, optionally substituted C ₆ -Cι ₀ aryl, an optionally substituted five- or six-membered aromatic or quasi-aromatic heterocyclic group, -OR ^6, -NH-R ⁶ or NR ⁶ R ⁷ or Y ² and Y ³ together represent a bridge,

R ⁶ and R ^7, independently of one another, for optionally substituted CC _J2 alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ - C] ₂ aralkyl, optionally substituted C ₆ -Cι ₀ aryl or a five- or six-membered hetero- cyclic ring stand or

NR ⁶ R ⁷ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals.

Azo compounds of the formula (Ic) are particularly preferred

wherein the ring A of the formula (IH)

N (HO

for benzthiazol-2-yl, which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, ethoxy, cyano or nitro, benzimidazol-2-yl, which can be substituted by up to three identical or different radicals of the series chlorine, methyl,

Methoxy, ethoxy, cyano or nitro can be substituted, thiazol-2-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, trifluoromethyl, methoxy, phenyl, cyano, nitro, methoxycarbonyl, methanesulfonyl, formyl or a bivalent radical of the formula - (CH ₂ ) - can be substituted, thiazol-4-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methoxy,

Methylthio, phenyl or cyano can be substituted, imidazol-2-yl, which can be substituted by up to two identical or different radicals from the series fluorine, chlorine, methyl, trifluoromethyl, methoxy, phenyl, cyano, nitro, CH ₃ 0- (C = NH) -, methoxycarbonyl or ethoxycarbonyl can be substituted, pyrazol-5-yl, which can be substituted by up to two identical or different radicals from the series chlorine, methyl, methoxy, phenyl, cyano or nitro, l, 3,4- Thiadiazol-2-yl, which is replaced by chlorine, bromine, methoxy, phenoxy, methanesulfonyl, methylthio, ethylthio, dimethylamino, diethylamino, di- (iso) -propylamino, N-methyl-N-cyanoethylamino, N, N-biscyanethylamino, N- Methyl-N-hydroxyethylamino, N-methyl-N-benzylamino, N-methyl-N-phenylamino, anilino, pyrrolidino, piperidino or morpholino can be substituted, l, 2,4-thiadiazol-5-yl by chlorine, methyl , Methoxy, phenoxy,

Methylthio, methanesulfonyl, phenyl, dimethylamino or anilino may be substituted, l, 2,4-thiadiazol-3-yl, which may be substituted by methyl or phenyl, 1,3,4-triazol-2-yl, which may be substituted by methyl or Phenyl may be substituted, 2-pyridyl which may be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 2-quinolyl which may be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 2-pyrimidyl which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 1,3,5-triazin-2-yl or 2-pyrazinyl,

in which

X ^{1 represents} O, S, NR ¹ or CH. R ^{1 represents} hydrogen, methyl, ethyl, propyl, butyl, allyl, benzyl, phenethyl or

Phenylpropyl stands,

R ^{2 and} R ³ independently of one another are hydrogen, methyl, ethyl, propyl, butyl,

Hydroxyethyl, cyanoethyl, cyclopentyl, cyclohexyl, allyl, benzyl, phenethyl, phenylpropyl, phenyl, tolyl, chloropehnyl or anisyl or

NR ² R ^{3 represents} pyrrolidino, piperidino or morpholino,

R ^{4 represents} hydrogen, chlorine, methyl, methoxy or methylthio,

R ^{5 is} hydrogen or methyl or

R ² ; R ⁴ and R ³ ; R ⁵ independently of one another are - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -C (CH ₃ ) ₂ -CH ₂ -CH (CH ₃ ) - or -0 (CH ₂ ) ₂ -,

Y stands for SOz-Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -NH-R ⁶ or -NR ⁶ R ⁷ ,

Y ² and Y ^{3 are the} same and represent methyl, ethyl, -OR ⁶ , -NH-R ⁶ or -NV or Y ² and

Y ³ together represent a - (CH ₂ ) ₄ bridge, or

Y ² for phenyl and

Y ^{3 represents} -OR ⁶ , -NH-R ⁶ or -M * R ⁷ ,

NR ⁶ R ^{7 represents} pyrrolidino, piperidino or morpholino.

The invention also relates to a process for the preparation of the azo compounds of the formula (Ic) according to the invention, which is characterized in that an amino heterocycle of the formula (IV)

wherein X ^{1 represents} O, S, NR ¹ or CH,

R ^{1 represents} hydrogen, optionally substituted CC ₁₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl or optionally substituted C ₇ -C ₂ aralkyl,

diazotized or nitrosed and onto a coupling component of the formula (V)

wherein

R ² and R ³ independently of one another for hydrogen, optionally substituted C ₁ -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C _{] 2} -

Alkenyl, optionally substituted C ₂ -C ₂ alkyl, optionally substituted C -

-C ₂ aralkyl, optionally substituted Cg-Cio-aryl or a five- or six-membered heterocyclic ring or

R ⁴ and R ⁵ independently of one another for hydrogen, halogen, optionally substituted Q-Cβ-alkyl, optionally substituted Cι-C ₆ alkoxy, optionally substituted Ci-Ce-

Alkylthio stand or

Y stands for S0 ₂ -Y 'or POY ² Y ³ , Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR'TR ⁷ ,

Y ² and Y ³ independently of one another for optionally substituted C 1 -C ₂ -alkyl, optionally substituted C 6 -C 10 -aryl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical, -OR ⁶ , -NH-R ⁶ or NR ^ ⁷ stand or Y ² and Y ³ stand together for a bridge,

R ⁶ and R ⁷ independently of one another for optionally substituted C ₁ -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C _{_7-Ci2} aralkyl, optionally substituted C ₆ -Cι ₀ aryl or a five- or six-membered hetero- cyclic ring stand or

NR ^ ⁷ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or which may be substituted by nonionic radicals,

couples.

Another object of the invention is a method for producing the invention

^" Azo compounds of the formula (Ic), characterized in that

that an amino heterocycle of the formula (IV)

embedded image in which

X ^{1 represents} NH,

diazotized or nitrosed and onto a coupling component of the formula (V)

embedded image in which

R ² and R ³ independently of one another for hydrogen, optionally substituted C ₁ -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₁₂ alkynyl, optionally substituted C ₇ -

C ₂ aralkyl, optionally substituted C ₆ -C ~ aryl or a five- or six-membered heterocyclic ring or

R ⁴ and R ^{5 are} independently hydrogen, halogen, optionally substituted Cj-C ₆ - alkyl, optionally substituted Cι-C ₆ -alkoxy, optionally substituted C] -C ₆ - alkylthio or

Y stands for SOz-Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ ,

Y ² and Y ³ independently of one another for optionally substituted -Ciz-alkyl, optionally substituted C ₆ -Cιo-aryl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical, -OR ⁶ , -NH-R ⁶ or NR '' TR ⁷ stand or Y ² and Y ³ stand together for a bridge,

R ⁶ and R ⁷ independently of one another for optionally substituted C ₁ -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -Ci ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ -C ₂ aralkyl, given appropriate, substituted C ₆ -Cι ₀ aryl or a five- or six-membered heterocyclic ring or

NR ^ R. ⁷ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and or which may be substituted by nonionic radicals,

couples,

and then with an alkylating agent of the formula

R'-Z (VI),

wherein

R represents optionally substituted C ₁ -C ₂ -alkyl, optionally substituted C ₃ -C ₈ cycloalyl, optionally substituted C ₂ -C ₂ alkenyl or optionally substituted C -C ₂ aralkyl,

and

Z represents a leaving group,

preferably in the presence of a basic substance.

R * -Z stands for example for an alkyl or aralkyl chloride, bromide, iodide, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, tolulsulfonate or a sulfuric acid alkyl or aralkyl ester. Examples are methyl iodide, benzyl bromide, dimethyl sulfate, toluenesulfonic acid ethyl ester.

The basic substances listed above are suitable as basic substances.

Diazotizations, nitrosations and couplings are known per se from the literature, e.g. from Chem. Ber. 1958, 91, 1025; Chem. Ber. 1961, 94, 2043; US-A 5,208,325. The procedures described there can be adopted in an analogous manner.

The amino heterocycles of the formulas IV to be used in the process according to the invention are known, for. B. from J. Polym. Be .: Part A: Polym. Chem. 1993, 31, 351, Chem. Ber. 1954, 87, 68;

Chem. Ber. 1956, 89, 1956, 2742; DE-OS 2 811 258.

The invention further relates to the coupling component of the formula (V)

embedded image in which

R ² and R ³ independently of one another for hydrogen, optionally substituted C] -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted

C ₇ -Cι ₂ -aralkyl, optionally substituted C ₆ -Cι ₀ aryl or a five- or six-membered heterocyclic ring or

R ⁴ and R ⁵ independently of one another represent hydrogen, halogen, optionally substituted C ₁ -C ₆ -alkyl, optionally substituted C ₁ -C ₆ -alkoxy, optionally substituted C ₁ -C ₆ -alkylthio or

Y stands for SOz-Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ ,

R ⁶ and R ⁷ independently of one another for optionally substituted C ₁ -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ -C ₂ aralkyl, given optionally substituted Cβ-Cio-aryl or a five- or six-membered heterocyclic ring or

NR'T ⁷ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals.

Preferred coupling components of the formula (V) are

wherein

R ^{6 represents} a fluorine-substituted ethyl, propyl or butyl radical, in particular 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2,2,3,3-tetrafluoropropyl, 1H, 1H-heptafluorobutyl, 1H, 1H, 4H-hexafluorobutyl and

R ^{7 is} methyl, ethyl or a fluorine-substituted ethyl, propyl or

Butyl radical stands in particular for 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2,2,3,3-tetrafluoropropyl, 1H, 1H-heptafluorobutyl, 1H, 1H, 4H-hexafluorobutyl.

The invention also relates to a process for the preparation of coupling components of the formula V, which is characterized in that

an m-phenylenediamine from Foπnel (VD

embedded image in which

R ² and R ³ independently of one another for hydrogen, optionally substituted C ₁ -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ -

Alkenyl, optionally substituted C ₂ -Ci ₂ -alkynyl, optionally substituted C ₇ -Ci ₂ aralkyl, optionally substituted C ₆ -C ₁₀ aryl or a five- or six-membered heterocyclic ring or NR ² R ³ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,

R ⁴ and R ⁵ independently of one another for hydrogen, halogen, optionally substituted Q- - alkyl, optionally substituted -Cβ-alkoxy, optionally substituted - -

Alkylthio stand or

with a sulfuric acid or phosphoric acid derivative of the formulas

Z ¹ -S0 ₂ -Y ¹ (VH) or

Z'-POY ² Y ³ (VIH)

wherein

Z ^{1 represents} chlorine or bromine,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ ,

Y and Y ³ independently represent optionally substituted Cι-Cι ₂ alkyl, optionally substituted C ₆ -Cι ₀ aryl, an optionally substituted five- or six-membered quasi-aromatic, or aromatic heterocyclic group, -OR ^6, -NH-R ⁶ or NR ^ ⁷ stand or Y ² and Y ³ stand together for a bridge,

R ⁶ and R ⁷ independently of one another for optionally substituted C 1 -C ₂ alkyl, optionally substituted -Cs cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ -C 4 _2- aralkyl, optionally substituted Cβ-cio-aryl or a five- or six-membered heterocyclic ring or

R ^ ⁷ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or which may be substituted by nonionic radicals,

implements. The invention also relates to a process for the preparation of coupling components of the formula V, in which Y represents POY ² Y ³ , which is characterized in that

an m-phenylenediamine of the formula (VI)

embedded image in which

R ² and R ³ independently of one another for hydrogen, optionally substituted Ci-Cπ-alkyl, optionally substituted C ₃ -C ₃ cycloalkyl, optionally substituted C ₂ -Cι ₂ -

Alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted

C ₇ -Ci ₂ aralkyl, optionally substituted -Cio-aryl or a five- or six-membered heterocyclic ring or

R ⁴ and R ⁵ independently of one another for hydrogen, halogen, optionally substituted Ci-Cg-alkyl, optionally substituted Cι-C ₆ alkoxy, optionally substituted Ci-Cg-

Alkylthio stand or

with a phosphinic acid derivative of the formulas

HPOY ² Y ³ (IX) or

P (OH) Y ² Y ³ (X),

wherein

Y ² and Y ³ independently of one another represent -OR ⁶ , -NH-R ⁶ or NR, R ⁶ and R ⁷ independently of one another for optionally substituted C] -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ -C ₁₂ aralkyl, optionally substituted C ₆ -C aro or a five- or six-membered heterocyclic ring or

NR ⁶ R ⁷ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,

in the presence of CCI ₄ or CBrCl ₃ .

The invention also relates to a process for the preparation of coupling components of the formula V, in which Y represents SOzY ¹ , which is characterized in that

an m-phenylenediamine of the formula (VI)

embedded image in which

R ² and R ³ independently of one another for hydrogen, optionally substituted C ₁ -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkyl, optionally substituted C ₇ -C ₂ aralkyl, optionally substituted C ₆ -C ₁₀ aryl or a five- or six-membered heterocyclic ring or

R ⁴ and R ⁵ independently of one another represent hydrogen, halogen, optionally substituted C 1 -C ₆ -alkyl, optionally substituted CC ₆ alkoxy, optionally substituted CC ₆ alkylthio or R ² ; R ⁴ and R ³ ; R ⁵ independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,

with chlorosulfonic acid and then with phosphorus pentachloride and this intermediate of the formula

wherein R ² to R ^{5 have} the meaning given above,

with an alcohol, phenol or amine of the formulas

HEAR ⁶ (XU),

H ₂ NR ⁶ (XIJJ) or

HNR ⁶ R ⁷ (XXV),

wherein

R ⁶ and R ⁷ independently of one another for optionally substituted C ₁ -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ -Cι ₂ -aralkyl, where appropriate substituted C ₆ -Cι ₀ aryl or a five- or six-membered heterocyclic ring or

implements.

R ³ and R ⁴ ≠ H are preferred for reaction. These reactions can be carried out in the presence of a base, for example a tertiary amine or a sodium or potassium hydroxide, hydrogen carbonate or carbonate.

The coupling component of the formula (V) is thus obtained in free form, as an HC1 or HBr salt.

Suitable solvents are 1,2-dichloroethane, carbon tetrachloride, toluene, but also alcohols such as methanol or ethanol and water.

From J. Chem. Soc. 1949, 2921; Dokl. Akad. Nauk SSSR, 96 (1954) 991; Phosphorus and Sulfur 1983, 155, coupling components of the formula (V) and processes for their preparation are known in some cases.

Sulfuric acid, phosphoric acid and phosphinic acid derivatives of the formulas (VII), (VIH), (IX) and (X) are known in some cases or can be prepared analogously: J. Fluorine Chem. 113 (2002)

65; J. Chem. Soc. 1949, 2921; J. Org. Chem. 41 (1976) 4028; Synthesis 1983, 63.

The preparation of sulfamic acid chlorides of the formula (XI) can be carried out analogously to J. Org. Chem. 41 (1976) 4028 or Chem. Ber. 120 (1987) 1191.

The invention further relates to the use of the metal complexes according to the invention as highly absorbent compounds in the hiformation layer of once writable optical

Media.

With this use, the optical data carrier is preferably written and read with blue laser light, in particular with a wavelength in the range of 360-460 nm.

With this use, the optical data carrier is also preferably written to and read with red laser light, in particular with a wavelength in the range from 600-700 nm.

The invention further relates to the use of metal complexes with azo ligands as a highly absorbent compound in the formation layer of write-once optical data carriers, the optical data carrier being able to be written and read with blue laser light, in particular with a wavelength in the range of 360-460 nm.

The invention further relates to an optical data carrier containing a preferably transparent substrate, optionally already coated with one or more reflective layers, on the surface of which an information layer which can be written on with light, optionally one or more reflective layers and optionally a protective layer or a further substrate or a covering layer are applied which is particularly preferred with a blue, preferably with a wavelength in the range of 360-460 nm, in particular 390 to 420 nm added from 400 to 410 nm, or red light, preferably with a wavelength in the range of 600-700 nm, preferably from 620 to 680 nm, very particularly preferably from 630 to 660 nm, preferably laser light, can be written and read, the Information layer contains a high-absorption compound and optionally a binder, characterized in that at least one according to the invention as the high-absorption compound

Metal complex is used.

The highly absorbent compound should preferably be thermally changeable. The thermal change preferably takes place at a temperature <600 ° C., particularly preferably at a temperature <400 ° C., very particularly preferably at a temperature <300 ° C., in particular <200 ° C. Such a change can be, for example, a decomposition or chemical change in the chromophoric center of the light-absorbing compound.

The preferred embodiment of the light-absorbing compounds in the optical data memory according to the invention correspond to the preferred embodiment of the metal complex according to the invention.

In a preferred form, the light-absorbing compounds used are those of the formulas (Ia) or (Ib),

wherein

X ^{1 represents} O, S, NR ¹ or CH,

R ^{1 represents} hydrogen, optionally substituted C ₁ -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl or optionally substituted C ₇ -C ₂ aralkyl,

R ² and R ³ independently of one another for hydrogen, optionally substituted C ₁ -C ₁₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ - Ciz-aralkyl, optionally substituted C ₆ -Cιo-aryl or a five- or six-membered heterocyclic ring or NR ² R ³ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,

Alkylthio stand or

Y stands for SO ₂ -Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ ,

Y ² and Y ³ independently of one another for optionally substituted C 1 -C ₂ -alkyl, optionally substituted C ₆ -C ₁₀ aryl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical, -OR ⁶ , -NH-R ⁶ or NR ^ ⁷ stand or Y ² and Y ³ stand together for a bridge,

R ⁶ and R ^7, independently of one another, for optionally substituted CrC ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ - C ₂ aralkyl, optionally substituted C ₆ -C ₀ aryl or a five- or six-membered heterocyclic ring or

M stands for a metal and

An ^"stands for an anion.

In a particularly preferred form, the light-absorbing compounds used are those of the formula (Ia)

wherein

the ring A of the formula (TU) ^N (HD '

for benzthiazol-2-yl, which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, ethoxy, cyano or nitro, benzimidazol-2-yl, which can be substituted by up to three identical or different radicals the series chlorine, methyl, methoxy, ethoxy, cyano or nitro can be substituted, thiazol-2-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, trifluoromethyl, methoxy, phenyl, cyano, nitro , Methoxycarbonyl, methanesulfonyl, formyl or a divalent radical of the formula - (CH) ₄ - can be substituted, thiazol-4-yl, which is replaced by up to two identical or different radicals from the series chlorine, fluorine, methoxy, methylthio, phenyl or cyano can be substituted, hnidazol-2-yl, which is substituted by up to two identical or different radicals from the series fluorine, chlorine, methyl, trifluoromethyl, methoxy, phenyl, cyano, nitro, CH ₃ 0- (C = NH) - , Methoxycarbonyl or ethoxycarbonyl may be substituted, pyrazol-5-yl, which can be substituted by up to two identical or different radicals from the series chlorine, methyl, methoxy, phenyl, cyano or nitro, l, 3,4-thiadiazol-2-yl, which is substituted by chlorine, bromine, methoxy, phenoxy, methanesulfonyl,

Methylthio, emylthio, dimethylamino, diethylamino, di (iso) propylamino, N-methyl-N-cyanoethylamino, N, N-biscyanethylamino, N-methyl-N-hydroxyethylamino, N-methyl-N-benzylamino, N-methyl- N-phenylamino, anilino, pyrrolidino, piperidino or morpholino can be substituted, l, 2,4-thiadiazol-3-yl, which can be substituted by methyl or phenyl, l, 2,4-thiadiazol-5-yl, by Chlorine, methyl, methoxy, phenoxy, methylthio,

Methanesulfonyl, phenyl, dimethylamino or anilino may be substituted, 1,3,4-triazol-2-yl, which may be substituted by methyl or phenyl, 2-pyridyl, which may be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro may be 2-quinolyl, which may be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 2-pyrimidyl, by up to three identical or different radicals from the series

Chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro can be substituted, 1,3,5-triazin-2-yl or 2-pyrazinyl is present,

in which

X ^{1 represents} O, S, NR ¹ or CH.

for hydrogen, methyl, ethyl, propyl, butyl, allyl, benzyl, phenethyl or

Phenylpropyl stands, R ² and R ³ independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, hydroxyethyl, cyanoethyl, cyclopentyl, cyclohexyl, allyl, benzyl, phenethyl, phenylpropyl, phenyl, tolyl, chloropehnyl or anisyl or

NR ² R ^{3 represents} pyrrolidino, piperidino or morpholino,

R ^{4 represents} hydrogen, chlorine, methyl, methoxy or methylthio,

R ^{5 represents} hydrogen or methyl or

R ² ; R ⁴ and R ³ ; R ⁵ independently of one another are - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -C (CH ₃ ) ₂ -CHz-CH (CH ₃ ) - or -0 (CH ₂ ) z-,

Y stands for SOz-Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -NH-R ⁶ or -NR ⁶ R ⁷ ,

Y ² and Y ^{3 are the} same and represent methyl, ethyl, -OR ⁶ , -NH-R ⁶ or -NR ⁶ R ⁷ or Y ² and Y ³ together represent a - (CH ₂ ) ₄ bridge or

Y ^{2 represents} phenyl and

Y ^{3 represents} -OR ⁶ , -NH-R ⁶ or -NR'Tt ⁷ ,

NR ^ ^{7 represents} pyrrolidino, piperidino or morpholino,

M stands for nickel, zinc, copper, cobalt, iron or palladium.

In a likewise particularly preferred form, the light-absorbing compounds used are those of the formula (Ib)

embedded image in which

the ring A of the formula (HT)

Methoxy, phenyl, cyano, nitro, methoxycarbonyl, methanesulfonyl, formyl or a bivalent radical of the formula - (CH ₂ ) ₄ - can be substituted, thiazol-4-yl, which can be substituted by up to two identical or different chlorine radicals , Fluorine, methoxy, methylthio, phenyl or cyano can be substituted, jmidazol-2-yl, which can be substituted by up to two identical or different radicals from the series fluorine, chlorine, methyl, trifluoromethyl,

Cyanethylamino, N, N-biscyanethylamino, N-methyl-N-hydroxyethylamino, N-methyl-N-benzylamino, N-methyl-N-phenylamino, anilino, pyrrolidino, piperidino or Moφholino can be substituted, l, 2,4-thiadiazole -3-yl, which can be substituted by methyl or phenyl, l, 2,4-thiadiazol-5-yl, which can be substituted by chlorine, methyl, methoxy, phenoxy, methylthio, methanesulfonyl, phenyl, dimethylamino or anilino, 1 , 3,4-triazole

2-yl, which can be substituted by methyl or phenyl, 2-pyridyl, which can be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 2-quinolyl, which can be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or Nitro can be substituted, 2-pyrimidyl, which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 1,3,5-

Triazin-2-yl or 2-pyrazinyl,

in which

X ^{1 represents} O, S, NR ¹ or CH.

R ² and R ³ independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, hydroxyethyl, cyanoethyl, cyclopentyl, cyclohexyl, allyl, benzyl, phenethyl, phenylpropyl, phenyl, tolyl, chlorophenyl or anisyl or NR ² R ^{3 represents} pyrrolidino, piperidino or Moφholino,

R ^{4 represents} hydrogen, chlorine, methyl, methoxy or methylthio,

R ^{5 represents} hydrogen or methyl or

Y stands for SOz-Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -NH-R ⁶ or -NR ⁶ R ⁷ ,

Y ³ together represent a - (CH ₂ ) ₄ bridge or

γ ^{2 represents} phenyl and

Y ^{3 represents} -OR ⁶ , -NH-R ⁶ or -NR ⁶ R ⁷ ,

NR ^ R ^{7 represents} pyrrolidino, piperidino or Moφholino,

M represents boron, aluminum or cobalt,

An ^"stands for iodide, nitrate, tetrafluoroborate, perchlorate, hexafluorophosphate, methanesulfonate, trifluoromethanesulfonate or the anion or an equivalent of an anion of a rhodamine, oxonol or azo metal complex dye.

For the once writable optical data carrier according to the invention, which is written and read with the light of a blue laser, such high-absorbing compounds are preferred whose absorption maximum A- ^ _x z is in the range 420 to 550 nm, the wavelength λ _1/2 , at which is the extinction in the short-wave flank of the absorption maximum of the wavelength λπ _m ώ half the extinction value at A - ^, and the wavelength λι _/ ι ₀ , at which the extinction in the short-wave flank of the absorption maximum of the wavelength λ _π ^

Is a tenth of the absorbance value at A ™ ^, preferably not more than 80 nm apart. Such a high-absorbency compound preferably has up to one Wavelength of 350 nm, particularly preferably up to 320 nm, very particularly preferably up to 290 nm, no shorter-wave maximum λ ^^.

Highly absorbent compounds with an absorption maximum λ _∞a a of 430 to 550 nm, in particular 440 to 530 nm, very particularly preferably 450 to 520 nm are preferred.

In the case of the highly absorbent compounds λy ₂ and λm ₀ , as defined above, the distances are preferably not more than 70 nm, particularly preferably not more than 50 nm, very particularly preferably not more than 40 nm.

For the once writable optical data carrier according to the invention, which is written and read with the light of a red laser, such highly absorbent compounds are preferred whose absorption maximum A _m ^ is in the range 500 to 650 nm, the

Wavelength λ) _{/ 2} , at which the absorbance in the long-wave flank of the absorption maximum of the wavelength is, and the wavelength λι ι ₀ , at which the extinction in the long-wave flank of the absorption maximum of the wavelength 7 ^^. is a tenth of the absorbance value at A ^^, preferably not more than 60 nm apart. Such a high-absorbency compound preferably has up to one

Wavelength of 750 nm, particularly preferably 800 nm, very particularly preferably 850 nm, no longer-wave maximum A -, ^ on.

Highly absorbent compounds with an absorption maximum A _n ^ of 510 to 620 nm are preferred.

Highly absorbent compounds with an absorption maximum are particularly preferred

A _maö from 530 to 610 nm.

Highly absorbent compounds with an absorption maximum A _m aö of 550 to 600 nm are very particularly preferred.

These high-absorption compounds λι _{/ 2} and λι _/ ι ₀ , as defined above, are preferably not more than 50 nm apart, particularly preferably not more than 40 nm apart, very particularly preferably not more than 30 nm apart.

At the absorption maximum A _ma ^, the highly absorbent compounds preferably have a molar extinction coefficient ε> 30,000 l / mol cm, preferably> 50,000 l / mol cm, particularly preferably> 70,000 l / mol cm, very particularly preferably> 100,000 l / mol cm.

The absorption spectra are measured, for example, in solution. Suitable highly absorbent compounds with the required spectral properties are, in particular, those which have a low solvatochromism (dioxane DMF or methylene chloride / methanol). Preferred are metal complexes whose solvatochromism Δλ _DD = | A _DMF - λ _D j _0xan |, ie the positive difference of the absorption wavelengths in the solvents dimethylformamide and dioxane, or whose solvatochromism ΔA _MM ⁼ IλMethanoi - λ _M ethyie _n c _h iorid |, ie the positive difference of the absorption wavelengths in the solvents methanol and methylene chloride, <20 nm, particularly preferably <10 nm, very particularly preferably <5 nm.

Preferred is the once writable optical data carrier according to the invention, which is written and read with the light of a red or blue, in particular red, laser.

The azo metal complexes according to the invention can also be used with other light-absorbing

Compounds are mixed. Highly absorbing compounds with similar spectral properties are preferably selected for this purpose. Such light-absorbing compounds can originate, for example, from the following classes of dyes: cyanines, (diaza) hemicyanines, merocyanines, rhodamines, azo dyes, polyphyrins, phthalocyanines, subphthalocyanines, azo metal complexes. Other azo metal complexes are preferred.

Other metal complexes are known, for example, e.g. from US-Bl 6,225,023.

The light-absorbing compounds used according to the invention guarantee a sufficiently high reflectivity (> 10%, in particular> 20%) of the optical data carrier in the blank state and a sufficiently high absorption for the thermal degradation of the information layer in the case of selective illumination with focused light if the light wavelength is in the

Range is from 360 to 460 nm and 600 to 680 nm. The contrast between written and unwritten points on the data carrier is realized by the change in reflectivity of the amplitude as well as the phase of the incident light by the optical properties of the information layer which have changed after thermal degradation.

The light-absorbing compounds used according to the invention have a high light resistance of the unwritten optical data carrier and of the information written on the data carrier against daylight, sunlight or under increased artificial radiation to imitate daylight.

The light-absorbing compounds used according to the invention also have a high sensitivity of the optical data carrier to blue and red laser light

Energy so that the data carrier can be written to at high speed (>2x,> 4x). The light-absorbing compounds used according to the invention are stable enough so that the disk produced with them generally fulfills the required climatic tests.

The metal complexes according to the invention are preferably applied to the optical data carrier by spin coating or vacuum evaporation, in particular spin coating. They can be mixed with one another or with other dyes with similar spectral properties. In addition to the metal complexes according to the invention, the information layer can contain additives such as binders, wetting agents, stabilizers, thinners and sensitizers and further constituents.

In addition to the information layer, the optical data storage device according to the invention can carry further layers such as metal layers, dielectric layers and protective layers. Metals and dielectric layers serve u. a. to adjust the reflectivity and the heat balance. Depending on the laser wavelength, metals can be gold, silver, aluminum and the like. a. his. Dielectric layers are, for example, silicon dioxide and silicon nitride. Protective layers are, for example, photocurable lacquers, (pressure-sensitive) adhesive layers and protective films.

Pressure-sensitive adhesive layers mainly consist of acrylic adhesives. Nitto Denko DA-8320 or DA-8310, disclosed in patent JP-A 11-273147, for example, can be used for this purpose.

The optical data carrier according to the invention has, for example, the following layer structure (cf. FIG. 1): a transparent substrate (1), optionally a protective layer (2), an information layer (3), optionally a protective layer (4), optionally an adhesive layer ( 5), one

Cover layer (6). The arrows shown in Fig. 1 and Fig. 2 represent the path of the light maintained.

The structure of the optical data carrier can preferably:

contain a preferably transparent substrate (1), on the surface of which at least one information layer (3) which can be written on with light and which can be written on with light, preferably laser light, optionally a protective layer (4), optionally an adhesive layer (5), and a transparent cover layer (6) are applied.

contain a preferably transparent substrate (1), on the surface of which a protective layer (2), at least one information layer (3) which can be written on with light, preferably laser light, optionally an adhesive layer (5), and a transparent cover layer (6) are applied , contain a preferably transparent substrate (1), on the surface of which there is optionally a protective layer (2), at least one information layer (3) that can be written on with light, preferably laser light, optionally a protective layer (4), optionally an adhesive layer (5), and a transparent cover layer (6) are applied.

- Contain a preferably transparent substrate (1), on the surface of which at least one information layer (3) which can be written on with light, preferably laser light, optionally an adhesive layer (5), and a transparent cover layer (6) are applied.

Alternatively, the optical data carrier has, for example, the following layer structure (cf. FIG. 2): a preferably transparent substrate (11), an information layer (12), optionally a reflection layer (13), optionally an adhesive layer (14), another preferably transparent substrate (15).

The invention further relates to optical data carriers according to the invention described with blue or red light, in particular laser light, in particular red laser light.

The following examples illustrate the subject matter of the invention.

Examples

example 1

a) 6.24 g of N, N-diethyl-m-phenylenediamine were dissolved in 50 ml of 1,2-dichloroethane under a nitrogen atmosphere. 6.4 g of N-propylamidosulfonic acid chloride were added, the temperature rising to 38 ° C. After stirring for 3 h at room temperature, the mixture was discharged into 200 ml of water and washed with 10% by weight. Sodium hydroxide solution adjusted to pH = 7.5. The organic phase was separated off, washed with 50 ml of water, dried over sodium sulfate and concentrated in a rotary evaporator. The oil obtained was extracted three times with 100 ml of methylcyclohexane. Finally, 6.1 g (56% of theory) of a brown oil of the formula remained

back.

b) 3.68 g of 2-amino-4,5-dicyano-imidazole were in a mixture of 110 ml of water and 18.4 ml of 35 wt. Hydrochloric acid suspended. 6.2 ml of a sodium nitrite solution, which contained 30 g of NaNO ₂ in 100 ml of water, dripped in at 1.5 ° C. for 1.5 h. The suspension was stirred for 1 h at 0-5 ° C with a clear excess of nitrite.

c) 6.08 g of the aniline derivative from a), 1.1 g of urea and 9.3 g of sodium acetate were placed in 250 ml of methanol. The diazotization prepared under b) was introduced at 0-5 ° C. for 1 h. The mixture was allowed to come to room temperature overnight with stirring. It was then suctioned off and dried at 60 ° C. in vacuo. 9.7 g (95% of theory) of the azo dye of the formula were obtained

as a red powder with a melting point of 180 ° C (sinters at 105-115 ° C).

λ- _nax = 494 nm (methanol)

ε = 31075 1 / mol cm.

d) 0.69 g was added to a solution of 2.15 g of the azo dye from c) in 50 ml of methanol

Dimethyl sulfate and 0.76 g of potassium carbonate at room temperature. After stirring for 2 hours at room temperature, 0.69 g of dimethyl sulfate and 0.76 g of potassium carbonate were again added. After stirring for a further 4 h, the product was filtered off with suction, washed with 2 × 5 ml of methanol and 100 ml of water and dried at 60 ° C. in vacuo. 1.0 g (45% of theory) of a copper-colored powder of the formula was obtained

from mp. 239-240 ° C (dec.).

λ- _nax = 512 nm (methanol)

ε = 48035 1 / mol cm.

e) 0.67 g of the dye from d) were suspended in 40 ml of methanol at room temperature.

0.19 g of nickel acetate tetrahydrate was added. Was overnight at room temperature stirred, suction filtered and dried at 50 ° C in a vacuum. 0.47 g (65% of theory) of a green powder of the formula were obtained

Mp> 290 ° C

_Π Q _X = 543 nm (chloroform)

ε = 106055 1 / mol cm

λiß-λi _/ io (long-wave flank) = 28 nm

Solubility:> 2% in TFP (2,2,3,3-tetrafluoropropanol)

glassy film

A further 0.1 g of metal complex of the above formula could be isolated by adding 2 ml of water to the mother liquor.

Example 2

a) 21.7 g of N, N-diethyl-m-phenylenediamine were dissolved in 100 ml of carbon tetrachloride.

49.1 g of bis (2,2,3,3-tetrafluoropropyl) phosphinic acid ester (produced according to J. Fluor. Chem. 113 (2002) 65) were added. After cooling to 0-5 ° C., a mixture of 25 ml of trichlorobromomethane and 25 ml of carbon tetrachloride was added dropwise at this temperature. The semicrystalline mass was stirred at about 10 ° C. for 1 hour and left to stand at room temperature overnight. It was diluted with 200 ml of carbon tetrachloride, suction filtered and washed with 50 ml of carbon tetrachloride. After drying at 40 ° C. in vacuo, 72.9 g (100% of theory) of a beige-pink powder of the formula were obtained

b) 20.0 g of 2-amino-4,5-dicyano-imidazole were in a mixture of 600 ml of water and 100 ml of 35 wt. Hydrochloric acid suspended. 33.5 ml of a sodium nitrite solution containing 30 g of NaNO ₂ in 100 ml of water dripped at 0-5 ° C. for 1.5 h. The suspension was stirred for 1 h at 0-5 ° C with a clear excess of nitrite, with 2 ml of the above sodium nitrite solution having to be added.

c) 64 g of the aniline derivative from a), 6 g of urea and 60 g of sodium acetate were placed in 650 ml of methanol. The diazotization prepared under b) was introduced at 0-5 ° C. for 1.5 h. The mixture was allowed to come to room temperature overnight with stirring. It was then filtered off, washed with 100 ml of water and dried at 60 ° C in a vacuum. 63.4 g (89% of theory) of the azo dye of the formula were obtained

as a brown powder with a melting point of 126-129 ° C.

λ- _n a _x = 491 nm (methanol)

ε = 37295 1 / mol cm.

d) 6.94 g of dimethyl sulfate dripped into a solution of 30.8 g of the azo dye from c) in 500 ml of methanol at room temperature for 1 h. After 1 h, 7.6 g of potassium carbonate were added. After stirring for 3 hours at room temperature, 6.94 g of dimethyl sulfate and 7.6 g of potassium carbonate were again added every hour. After stirring for a further 4 h, the product was filtered off with suction, washed with 3 × 10 ml of methanol and 250 ml of water and dried at 60 ° C. in vacuo. 19.5 g (62% of theory) of a bordeaux-red powder of the formula were obtained

of melting point 200 ° C.

λ _max = 519 nm (methanol)

ε = 55822 1 / mol cm.

e) 2 g of the dye from d) were suspended in 70 ml of methanol at room temperature. 0.39 g of nickel acetate tetrahydrate was added. A deep red solution was formed, from which product precipitated when stirred overnight. It was filtered off and dried at 50 ° C in a vacuum. 0.94 g (44% of theory) of a green powder of the formula were obtained

Mp 249 ° C

λ _max = 540 nm (chloroform)

ε = 106 024 1 / mol cm

λι ₂ -λι / ιo (long-wave flank) = 24 nm

Solubility:> 2% in TFP (2,2,3, 3-tetrafiuoφropanol)

glassy film

By adding 3 ml of water to the mother liquor, a further 0.95 g of metal complex of the above formula, but in a lower purity, could be isolated.

Suitable azometal dyes are listed in the following table:

Formula (Ia)

ΔA - lA ethylene chloride "A] y [ethanol]

³⁾ on the long-wave flank

⁴⁾ in methanol ⁵⁾ in chloroform

Example 57

a) 41 g of N, N-diethyl-m-phenylenediamine were dissolved in 350 ml of 1,2-dichloroethane under a nitrogen atmosphere. 35.9 g of dimethylamidosulfonic acid chloride were added. After stirring for 24 h at room temperature, 27.7 g of triethylamine and 10 g of dimethyl amidosulfonic acid chloride were added and the mixture was again stirred at room temperature for 24 h. It was discharged into 1000 ml of water and with 10% by weight. Sodium hydroxide solution adjusted to pH = 7.5. The organic phase was separated, washed with 100 ml of water, dried over sodium sulfate and evaporated. The oil obtained was extracted three times with 100 ml of methylcyclohexane. Finally, 47.1 g (61% of theory) of a brown oil of the formula remained

back.

b) 3.26 g of 3-phenyl-5-amino-l, 2,4-thiadiazole were dissolved in a mixture of 30 ml of glacial acetic acid and 15 ml of formic acid. A solution of 1.28 g of sodium nitrite in 10 ml of water was slowly added dropwise at 0-5 ° C. After 2 h at 0-5 ° C., a solution of 5 g of the m-phenylenediamine derivative from a) in 20 ml of glacial acetic acid was slowly added. It was warmed to room temperature and finally carefully heated to 90-95 ° C. After 1 h, the mixture was cooled, suction filtered and dried. 3.4 g (40% of theory) of a red dye of the formula were obtained

A _max = 519 nm (in methylene chloride).

c) 0.14 g of cobalt (I [) acetate tetrahydrate were placed in 10 ml of acetone and with 5 drops

65 percent strength. Nitric acid added. After 1 h, this solution was added to a solution of 0.5 g of the dye from b) in 10 ml of acetone and stirred at 60 ° C. for 1 h. After cooling, it was discharged into a solution of 0.5 g of lithium perchlorate in 20 ml of water.

The precipitated dye was filtered off with suction: 0.44 g (82% of theory). It has the formula

Mp = 195 ° C

Electrospray mass spectrum: m / e = 975

A _max ⁼ 553 nm (in methylene chloride)

ε = 53510 1 / mol cm

λι _{/ 2} - ιo (long-wave flank) = 42 nm

Solubility:> 2% in TFP (2,2,3,3-tetrafluoropropanol)

glassy film

Suitable azometal dyes are listed in the following table:

Formula (Ib)

n etyenc or, if nc t indicated to ers.

2)

ΔA | AMethyIencWorid ~ Methanoll

³⁾ on the long-wave flank

Example 71

A solution of 2.2 g of dye 1 in 100 ml of 2,2,3,3-tetrafluoropropanol was prepared at room temperature. This solution was applied to a pregrooved polycarbonate substrate using spin coating. The pregrooved polycarbonate substrate was produced as a disk using injection molding. The dimensions of the disc and the groove structure corresponded to those which are usually used for DVD-R. The disk with the dye layer as the information carrier was sputtered with 100 nm silver. A UV-curable acrylic lacquer was then applied by spin coating and cured using a UV lamp. The Dist was tested with a dynamic writing test set-up on an optical bench, consisting of a diode laser (λ = 656 nm), for generating linearly polarized light, a polarization-sensitive beam splitter, a λ / 4 plate and a movably suspended converging lens a numerical aperture NA = 0.6 (actuator lens). The light reflected by the reflection layer of the disk was coupled out of the beam path with the aid of the polarization-sensitive beam splitter mentioned above and focused on a four-quadrant detector by an astigmatic lens. At a linear speed

V - 3.5 m / s and a write power P _1w - _te = 10 mW, a signal-to-noise ratio C / N = 51.5 dB was measured for HT pits. The write power was applied here as an oscillating pulse sequence (cf. FIG. 3), the disk being alternately irradiated with the above-mentioned write power P- _mU e and the _{read power} P _read * 0.5 mW. The write pulse sequence for the HT pit consisted of a leading pulse of length T _top = 1.57 ^* = 60 ns, where T- 40 ns is the base time

(11T = 440 ns). The leading pulse was placed in such a way that it ended after S units. This was followed by eight pulses of length T _mp = 30 ns, the time being determined by T _mp = 0.757 ". This means that there is a time period ΛT = 10 ns between each write pulse. The 117 ^* long write pulse was followed by a \ \ T long pause The disk was irradiated with this oscillating pulse sequence until it had rotated once around itself, after which the marking thus generated was _read out with the reading power P _read and the above-mentioned signal-to-noise ratio C / N measured.

Example 72

Analogously to Example 71, a solution of 1.8 g of dye 11 in 100 ml of 2,2,3,3-tetrafluoropropanol was prepared at room temperature and a disk was produced as in Example 71 and burned in the same structure. Under the same conditions, a signal-to-noise ratio C / N = 48 dB was measured at a write power of 10mW. Example 73

Analogously to Example 71, a solution of 2.2 g of dye 15 in 100 ml of 2,2,3,3-tetrafluoropropanol was prepared at room temperature and a disk was produced as in Example 71 and burned in the same structure. Under the same conditions, a signal-to-noise ratio C / N = 53 dB was measured at a write power of 10mW.

Analogous results were obtained with the metal complexes of the other examples listed above.

Claims

claims

1. metal complexes which have at least one ligand of the formula (I),

embedded image in which

X ^{1 represents} O, S, NR ¹ or CH,

R ¹ is hydrogen, optionally substituted -C ^ alkyl, optionally substituted C3-C ₈ -cycloalkyl, optionally substituted C ₂ -CJ ₂ alkenyl or optionally substituted C ₇ -Cι ₂ is aralkyl,

R ² and R ³ independently of one another for hydrogen, optionally substituted C ₁ -C ₁₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ - Alkynyl, optionally substituted optionally substituted C ₆ -C ₁₀ aryl or a five- or six-membered heterocyclic ring or

R ⁴ and R ⁵ independently of one another represent hydrogen, halogen, optionally substituted CC ₆ alkyl, optionally substituted Ci-C _ö alkoxy, optionally substituted -Cβ-alkylthio or R ² ; R ⁴ and R ³ ; R ^s independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,

Y stands for SOz-Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ ,

Y ² and Y ³ independently is optionally substituted _{Cι-Ci2-alkyl,} optionally substituted C ₆ -Cι ₀ aryl, an optionally substituted five- or six-membered aromatic or quasi-aromatic heterocyclic group,

-OR ⁶ , -NH-R ⁶ or R ^ ⁷ or Y ² and Y ³ together represent a bridge,

R ^δ and R ⁷ independently of one another for optionally substituted C ₁ -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₁₂ alkenyl, optionally substituted C ₂ -C ₁₂ alkynyl, optionally substituted C ₇ -Cj ₂ aralkyl, optionally substituted C ₆ -Cιo aryl or a five- or six-membered heterocyclic ring or

or metal complexes which have at least one ligand of the formula (LI)

embedded image in which

X ^{2 represents} N or CH

and the other radicals have the meaning given above.

2. Metal complexes according to claim 1, characterized in that they contain two identical or different ligands of the formula (ϊ) or (LI).

3. Metal complexes according to at least one of claims 1 to 2, characterized in that they have the formula (Ia)

[(')] ^" M ^{2+ (Ia} >

correspond in which the two ligands of the formula (I) independently of one another have the meaning given in claim 1 and

M stands for a metal, or

of the formula (Ib)

(I) M ³⁺ Arr (Ib)

correspond, in which the two ligands of the formula (D independently of one another have the meaning given above and

M stands for a metal and

An ^"stands for an anion.

4. Metal complexes according to at least one of claims 1 to 3, characterized in that they have the formula (Ia)

[(")] ^" _M ^{2+ (Ia)}

2

M stands for a metal.

5. Metal complexes according to at least one of claims 1 to 4, characterized in that the metal is a divalent metal, transition metal or rare earth, especially Mg, Ca, Sr, Ba, Cu, Ni, Co, Fe, Zn, Pd, Pt, Ru, Rh, Th, Os, Sm, Eu.

6. Metal complexes according to at least one of claims 1 to 5, characterized in that the metal is Pd, Fe, Zn, Cu, Ni or Co.

7. Metal complexes according to at least one of claims 1 to 6, characterized in that the metal is a trivalent metal, transition metal or rare earth, in particular B, Al, Ga, In, V, Co, Cr, Fe, Y, La, Ce , Pr, Nd, Sm, Eu, Gd, Tb.

- 8. Metal complexes according to at least one of claims 1 to 7, characterized in that the metal is B, Al or Co.

9. Metal complexes according to at least one of claims 1 to 8, characterized in that in the formula (ϊ)

the ring A of the formula (DT)

for benzthiazol-2-yl, which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, ethoxy, cyano or nitro,

Benzimidazol-2-yl, which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, ethoxy, cyano or nitro, thiazol-2-yl, which can be substituted by up to two identical or different radicals from the Series chlorine, fluorine, methyl, trifluoromethyl, methoxy, phenyl, cyano, nitro, methoxycarbonyl, methanesulfonyl, formyl or a divalent radical of the formula

- (CH ₂ ) - can be substituted, thiazol-4-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methoxy, methylthio, phenyl or cyano, imidazol-2-yl, by up to two identical or different radicals from the series fluorine, chlorine, methyl, trifluoromethyl, methoxy, phenyl, cyano, nitro, CH ₃ 0- (C = NH) -, methoxycarbonyl or

Ethoxycarbonyl can be substituted, pyrazol-5-yl, which can be substituted by up to two identical or different radicals from the series chlorine, methyl, methoxy, phenyl, cyano or nitro, 1,2,4-thiadiazol-3-yl, which can be substituted by methyl or phenyl, l, 3,4-thiadiazol-2-yl, which by chlorine, bromine, methoxy, phenoxy, methanesulfonyl, methylthio, ethylthio, dimethylamino, Diethylamino, di (iso) propylamino, N-methyl-N-cyanoethylamino, N, N-bis-cyanoethylamino, N-methyl-N-hydroxyethylamino, N-methyl-N-benzylamino, N-methyl-N-phenylamino, Anilino, pyrrolidino, piperidino or morpholino can be substituted, l, 2,4-thiadiazol-5-yl, which can be substituted by chlorine, methyl, methoxy, phenoxy, methylthio, methanesulfonyl, phenyl, dimethylamino or anilino, l, 3, 4-triazol-2-yl, which can be substituted by methyl or phenyl, 2-pyridyl, which can be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 2-quinolyl, which can be substituted by chlorine, methyl, methoxy, Cyano, methoxycarbonyl or nitro can be substituted, 2-pyrimidyl by up to three identical or different radicals from the series

Chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro can be substituted, l, 3,5-triazin-2-yl or 2-pyrazinyl,

in which

X ^{1 represents} O, S, NR ¹ or CH.

R ^{1 represents} hydrogen, methyl, ethyl, propyl, butyl, allyl, benzyl, phenethyl or

Phenylpropyl stands,

R ² and R ³ independently of one another are hydrogen, methyl, ethyl, propyl, butyl,

Hydroxyethyl, cyanoethyl, cyclopentyl, cyclohexyl, allyl, benzyl, phenethyl, phenylpropyl, phenyl, tolyl, chlorophenyl or anisyl or

NR ² R ^{3 represents} pyrrolidino, piperidino or morpholino,

R ^{4 represents} hydrogen, chlorine, methyl, methoxy or methylthio,

represents hydrogen or methyl or

R ² ; R ⁴ and R ³ ; R ⁵ independently of one another represent - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -C (CH ₃ ) ₂ -CH ₂ - CH (CH ₃ ) - or -0 (CH ₂ ) ₂ -,

Y stands for SO ₂ -Y ¹ or P0Y ² Y ³ ,

Y ^{1 represents} -NH-R ⁶ or -NR ⁶ R ⁷ ,

Y ² and Y ^{3 are the} same and represent methyl, ethyl, -OR ⁶ , -NH-R ⁶ or -NRV or Y ² and Y ³ together represent a - (CH ₂ ) ₄ bridge or

Y ^{2 represents} phenyl and Y ^{3 represents} -OR ⁶ , -NH-R ⁶ or -NR ^ ⁷ ,

R ⁶ and R ⁷ independently of one another are methyl, ethyl, propyl, butyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2,2,3,3-tetrafluoropropyl, 1H, 1H-heptafluorobutyl, 1H, 1H, 4H-hexafluorobutyl, cyclohexyl, allyl, benzyl or phenyl or

NR ⁶ R ^{7 represents} pyrrolidino, piperidino or morpholino,

M stands for nickel, zinc, copper, cobalt, iron or palladium or

M stands for boron, aluminum or cobalt and

10. Metal complexes according to at least one of claims 1 to 9, characterized in that

the ring A of the formula (IH)

for benzthiazol-2-yl, chlorobenzthiazol-2-yl, methylbenzthiazol-2-yl, methoxybenzthiazol-2-yl or nitrobenzthiazol-2-yl, benzimidazol-2-yl, thiazol-2-yl, phenylthiazol-2-yl , Cyanothiazol-2-yl, nitrothiazol-2-yl, 5-fluoro-4-trifluoromethylthiazol-2-yl, 5-phenyl-4-trifluoromethylthiazol-2-yl, 2-methylthio-5-cyano-thiazol-4 -yl, imidazol-2-yl, 4,5-diphenylimidazol-2-yl, 4,5-dicyanoimidazol-2-yl, 4,5-bis-methoxycarbonylimidazol-2-yl or 4,5-bis-ethoxycarbonylimidazol-2 yl,

Pyrazol-5-yl, l, 3,4-thiadiazol-2-yl, 5-phenoxy-l, 3,4-thiadiazol-2-yl, 5-methylthio-l, 3,4-thiadiazol-2-yl, 5-dimethylamino-l, 3,4-thiadiazol-2-yl, 5-diethylamino-l, 3,4-thiadiazol-2-yl, 5-di- (iso) -propylamino-l, 3,4-thiadiazol- 2-yl, 5-N-methyl-N-cyanoethylamino-l, 3,4-thiadiazol-2-yl, 5-pyrrolidino-l, 3,4-thiadiazol-2-yl, 5-phenyl-l, 3, 4-thiadiazol-2-yl, 5-methyl-l, 3,4-thiadiazol, l, 2,4-thiadiazol-5-yl, 3-

Methylthio-l, 2,4-thiadiazol-5-yl, 3-methanesulfonyl-l, 2,4-thiadiazol-5-yl,

3-phenyl-l, 2,4-thiadiazol-5-yl, l, 3,4-triazol-2-yl, 2-pyridyl, 2-quinolyl, 2-pyrimidyl, 4-cyano-2-pyrimidyl, 4, 6-dicyano-2-pyrimidyl, l, 3,5-triazin-2-yl or 2-pyrazinyl, in which

X ^{1 represents} O. S- NR ¹ or CH,

R ^{1 represents} hydrogen, methyl, ethyl or benzyl,

NR ² R ^{3 represents} pyrrolidino, piperidino or morpholino,

R ^{4 represents} hydrogen, methyl or methoxy,

R ^{5 represents} hydrogen or

R ² ; R ^{4 represents} - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ -,

Y stands for SO ₂ -Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -NH-R ⁶ or -NR ⁶ R ⁷ ,

Y ² and Y ^{3 are the} same and stand for -OR ⁶ ,

R ⁶ and R ⁷ independently of one another represent methyl, ethyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2,2,3,3-tetrafluoropropyl, benzyl or phenyl or

NR ⁶ R ^{7 represents} pyrrolidino, piperidino or morpholino,

M stands for nickel, zinc, copper or cobalt or

M stands for cobalt and

stands.

11. A process for the preparation of metal complexes according to claim 1, characterized in that a metal salt with an azo compound of the formula (Ic)

embedded image in which

X ^{1 represents} O, S, NR ¹ or CH,

R ¹ is hydrogen, optionally substituted Ci C ₂ alkyl optionally substituted _C3-C8 cycloalkyl, optionally substituted C ₂ -C ₁₂ alkenyl or optionally substituted C ₇ -Cι ₂ is aralkyl,

R ² and R ³ independently of one another for hydrogen, optionally substituted C ₁ -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ -C ₂ aralkyl, optionally substituted C ₆ -C aro or a five- or six-membered heterocyclic ring or

R ⁴ and R ⁵ independently of one another represent hydrogen, halogen, optionally substituted C ₁ -C ₆ -alkyl, optionally substituted C] -C ₆ -alkoxy, optionally substituted CC ₆ -alkylthio or

Y stands for SÜ ₂ -Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ ,

Y ² and Y ³ independently of one another for optionally substituted optionally substituted Cβ-cio-aryl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical, -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ or Y ² and Y ³ together represent a bridge,

R ⁶ and R ⁷ independently of one another for optionally substituted C 1 -C ₂ -alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -Cj ₂ -

Alkenyl, optionally substituted C ₂ -C] ₂ alkynyl, optionally substituted C ₇ -Cι ₂ -aralkyl, optionally substituted C ₆ -Cι are ₀ or aryl, or a five or six membered heterocyclic ring

NR'Ti ⁷ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,

implements.

12. Use of metal complexes according to at least one of claims 1 to 10 as a light-absorbing compound in the information layer of write-once optical data carriers.

13. Use according to claim 12, characterized in that the optical data carrier with blue laser light, in particular with a wavelength in the range of 360-460 nm, can be written and read.

14. Use according to at least one of claims 12 or 13, characterized in that the optical data carrier with red laser light, in particular with a wavelength in

Range of 600-700 nm can be written and read.

15. Use of metal complexes with azo ligands as light-absorbing compounds in the information layer of write-once optical data carriers, the optical data carrier being able to be written and read with blue laser light, in particular with a wavelength in the range of 360-460 nm.

16. Azo compounds of the formula (Ic)

embedded image in which

X ^{1 represents} O, S, NR ¹ or CH,

A together with X ¹ and N represents a five- or six-membered aromatic or quasi-aromatic heterocyclic ring which contains 1 to 4 heteroatoms and or can be benzylated or naphthanellated and / or substituted by nonionic radicals,

R ^{1 represents} hydrogen, optionally substituted -C ^ alkyl, optionally substituted, substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl or optionally substituted C ₇ -C ₂ aralkyl,

R ² and R ³ independently of one another for hydrogen, optionally substituted C 1 -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₁₂ alkynyl, optionally substituted C ₇ -Cι, standing or optionally substituted C ₆ -Cι ₀ aryl or a five- or six-membered heterocyclic ring ₂ -aralkyl NR ² R ³ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,

R ⁴ and R ^s are independently hydrogen, halogen, optionally substituted -C _ö alkyl optionally substituted Cι-C ₆ -alkoxy, unsubstituted or substituted Cι-C ₆ alkylthio, or are

R ² ; R ⁴ and R ³ R ⁵ independently of one another represent a two- to four-membered bridge which can contain further heteroatoms and / or can be substituted by nonionic radicals,

Y stands for SO ₂ -Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ ,

Y ² and Y ³ independently is optionally substituted Cι-Cι ₂ alkyl, optionally substituted C ₆ -Cι ₀ aryl, an optionally substituted five- or six-membered quasi-aromatic, or aromatic heterocyclic group, -OR ^6, -NH-R ⁶ or NR ⁶ R ⁷ stand or Y ² and Y ³ together stand for a bridge,

R ⁶ and R ⁷ independently of one another for optionally substituted C ₁ -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -

C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ -Ci ₂ aralkyl, optionally substituted Cβ- o-aryl or a five- or six-membered heterocyclic ring or

17. Azo compounds according to claim 16, characterized in that in formula (Ic),

the ring A of the formula (DT)

( ^AX V- m for benzothiazol-2-yl, which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, ethoxy, cyano or nitro, benzimidazol-2-yl, which can be substituted by up to three identical or different radicals the series chlorine, methyl, methoxy, ethoxy, cyano or nitro can be substituted, thiazol-2-yl, which can be substituted by up to two identical or different radicals from the series

Chlorine, fluorine, methyl, trifluoromethyl, methoxy, phenyl, cyano, nitro, methoxycarbonyl, methanesulfonyl, formyl or a bivalent radical of the formula - (CH ₂ ) - can be self-substituted, thiazol-4-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methoxy, methylthio, phenyl or cyano can be substituted, imidazol-2-yl, which is replaced by up to two identical or different radicals from the series fluorine, chlorine, methyl, trifluoromethyl, methoxy, phenyl, Cyano, nitro, CH ₃ 0- (C = NH) -, methoxycarbonyl or ethoxycarbonyl can be substituted, pyrazol-5-yl, which can be substituted by up to two identical or different radicals from the series chlorine, methyl, methoxy, phenyl, cyano or Nitro can be substituted, l, 3,4-thiadiazol-2-yl, which is replaced by chlorine, bromine, methoxy,

Phenoxy, methanesulfonyl, methylthio, ethylthio, dimethylamino, diethylamino, di- (iso) propylamino, N-methyl-N-cyanoethylamino, N, N-biscyanethylamino, N-methyl-N-hydroxyethylamino, N-methyl-N-benzylamino, N-methyl-N-phenylamino, anilino, pyrrolidino, piperidino or morpholino can be substituted, 1,2,4-thiadiazol-3-yl, which can be substituted by methyl or phenyl, 1,2,4-

Thiadiazol-5-yl, which can be substituted by chlorine, methyl, methoxy, phenoxy, methylthio, methanesulfonyl, phenyl, dimethylamino or anilino, 1,3,4-triazol-2-yl, which can be substituted by methyl or phenyl, 2-pyridyl, which can be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 2-quinolyl, which can be substituted by chlorine, methyl, methoxy, cyano,

Methoxycarbonyl or nitro can be substituted, 2-pyrimidyl, which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, l, 3,5-triazin-2-yl or 2-pyrazinyl is,

in which

X ^{1 represents} O, S, NR ¹ or CH.

represents hydrogen, methyl, ethyl, propyl, butyl, allyl, benzyl, phenethyl or phenylpropyl, - 16 -

NR ² R ^{3 represents} pyrrolidino, piperidino or Moφholino,

R ^{4 represents} hydrogen, chlorine, methyl, methoxy or methylthio,

R ^{5 is} hydrogen or methyl or

Y stands for SOa-Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -NH-R ⁶ or -NR ⁶ R ⁷ ,

Y ² and Y ^{3 are the} same and represent methyl, ethyl, -OR ⁶ , -NH-R ⁶ or -NR ⁶ R ⁷ or Y ² and Y ^{3 represent} a - (CH ₂ ) ₄ bridge or

Y ^{2 represents} phenyl and

Y ^{3 represents} -OR ⁶ , -NH-R ⁶ or -NR ⁶ R ⁷ ,

R ⁶ and R ⁷ independently of one another for methyl, ethyl, propyl, butyl, 2,2,2-

Trifluoroethyl, 2,2-difluoroethyl, 2,2,3,3-tetrafluoropropyl, 1H, 1H-heptafluorobutyl, 1H, 1H, 4H-hexafluorobutyl, cyclohexyl, allyl, benzyl or phenyl or

NR ⁶ R ^{7 stands} for pyrrolidino, piperidino or Moφholino.

18. Azo compounds according to claim 16 or 17, characterized in that

the ring A of the formula (IH)

(7 \ - (TU)

N

for benzthiazol-2-yl, chlorobenzthiazol-2-yl, methylbenzthiazol-2-yl, methoxybenzthiazol-2-yl or nitrobenzthiazol-2-yl, benzimidazol-2-yl, thiazol-2-yl,

Phenylthiazol-2-yl, cyanothiazol-2-yl, nitrothiazol-2-yl, 5-fluoro-4-trifluoromethylthiazol-2-yl, 5-phenyl-4-trifluoromethylthiazol-2-yl, 2-methylthio-5- cyano- thiazol-4-yl, hnidazol-2-yl, 4,5-diphenylimidazol-2-yl, 4,5-dicyanoimidazol-2-yl, 4,5-bis-methoxycarbonylimidazol-2-yl or 4,5-bis- ethoxycarbonylimidazol-2-yl, pyrazol-5-yl, l, 3,4-thiadiazol-2-yl, 5-phenoxy-l, 3,4-thiadiazol-2-yl, 5-methylthio-l, 3,4- thiadiazol-2-yl, 5-dimethylamino-l, 3,4-thiadiazol-2-yl, 5-diethylamino-l, 3,4-thiadiazol-2-yl, 5-di- (iso) -propylamino-l, 3,4-thiadiazol-2-yl, 5-N-methyl

N-cyanoethylamino-l, 3,4-thiadiazol-2-yl, 5-pyrrolidino-l, 3,4-thiadiazol-2-yl, 5- phenyl-l, 3,4-thiadiazol-2-yl, 5- Methyl-l, 3,4-thiadiazol, l, 2,4-thiadiazol-5-yl, 3-methylthio-l, 2,4-thiadiazol-5-yl, 3-methanesulfonyl-l, 2,4-thiadiazol- 5-yl, 3-phenyl-l, 2,4-thiadiazol-5-yl, l, 3,4-triazol-2-yl, 2-pyridyl, 2-quinolyl, 2-pyrimidyl, 4-cyano-2- pyrimidyl, 4,6-dicyano-2-pyrimidyl, l, 3,5-triazin-2-yl or

2-pyrazinyl is,

in which

X ^{1 represents} O, S, NR ¹ or CH,

R ^{1 represents} hydrogen, methyl, ethyl or benzyl,

NR ² R ^{3 represents} pyrrolidino, piperidino or Moφholino,

R ^{4 represents} hydrogen, methyl or methoxy,

R ^{5 represents} hydrogen or

R ² ; R ^{4 represents} - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ -,

Y stands for SOz-Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -NH-R ⁶ or -NR ⁶ R ⁷ ,

Y ² and Y ^{3 are the} same and stand for -OR ⁶ ,

R ^{6 and} R ⁷ independently of one another represent methyl, ethyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2,2,3,3-tetrafluoropropyl, benzyl or phenyl or

NR ⁶ R ^{7 represents} pyrrolidino, piperidino or Moφholino,

19. A process for the preparation of azo compounds of the formula (Ic) according to claim 15, characterized in that an amino heterocycle of the formula (TV)

embedded image in which

X ^{1 represents} O, S, NR ¹ or CH,

R ^{1 represents} hydrogen, optionally substituted C] -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₁₂ alkenyl or optionally substituted C ₇ -C ₂ aralkyl,

diazotized or nitrosed and onto a coupling component of the formula (V)

wherein

R ² and R ³ independently of one another for hydrogen, optionally substituted -C ₁₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ -Cι ₂ -aralkyl, optionally substituted C ₆ -Cι ₀ aryl or a five- or six-membered heterocyclic ring or

NR ² R ³ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals, R ⁴ and R ^{5 are} independently hydrogen, halogen, optionally substituted CC ₆ alkyl, optionally substituted Cι-C _β alkoxy, optionally substituted Cι-C are ₆ alkylthio, or

Y stands for SOz-Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ^ ⁷ ,

Y ² and Y ³ independently of one another for optionally substituted optionally substituted Cβ-cio-aryl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical, -OR, -NH-R or NR R or Y and Y together represent a bridge,

R ⁶ and R ⁷ independently of one another are optionally substituted -C ^ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -

Cι ₂ alkenyl optionally substituted C, ₂ -Cι ₂ -alkynyl, optionally substituted C ₇ -Cι ₂ -aralkyl, optionally substituted C ₆ -Cι are ₀ or aryl, or a five or six membered heterocyclic ring

couples.

20. A process for the preparation of azo compounds of the formula (Ic) according to claim 15, characterized in that an amino heterocycle of the formula (TV)

embedded image in which

X ^{1 represents} NH A together with X ¹ and N represents a five- or six-membered aromatic or quasi-aromatic heterocyclic ring which contains 1 to 4 heteroatoms and / or benzylated or naphthanellated and / or can be substituted by nonionic radicals,

diazotized or nitrosed and onto a coupling component of the formula (V)

wherein

R ² and R ³ independently of one another for hydrogen, optionally substituted C ₁ - ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl , optionally substituted C ₇ -C ₂ aralkyl, optionally substituted Cβ-Cjo-aryl or a five- or six-membered heterocyclic ring or

R ⁴ and R ⁵ independently of one another represent hydrogen, halogen, optionally substituted Ci-Cβ-alkyl, optionally substituted Cι-C ₆ alkoxy, optionally substituted Ci-Ce-alkylthio or

Y stands for SO ₂ -Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ ,

Y ² and Y ³ independently of one another for optionally substituted C 1 -C ₂ alkyl, optionally substituted C ₆ -C ₀ aryl, an optionally substituted five or six-membered quasi-aromatic or aromatic heterocyclic radical, -OR ⁶ , -NH-R ⁶ or NR ' ⁷ or Y ² and Y ³ together represent a bridge,

R ⁶ and R ⁷ independently of one another for optionally substituted C 1 -C ₂ -alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -

NR'TR ⁷ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,

couples,

and then with an alkylating agent of the formula

R ^] -Z (VI),

wherein

R represents optionally substituted C 1 -C ₂ -alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl or optionally substituted C ₇ -C ₂ aralkyl,

and

Z represents a leaving group,

preferably in the presence of a basic substance.

22. Coupling components of the formula (V)

wherein

R ² and R ³ independently of one another for hydrogen, optionally substituted C 1 -C ₂ -alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -d ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, if substituted C ₇ -C ₁₂ aralkyl, optionally substituted Cβ-Cjo-aryl or a five- or six-membered heterocyclic ring or

R ⁴ and R ⁵ independently of one another for hydrogen, halogen, optionally substituted

Ci-Cβ-alkyl, optionally substituted CC ₆ -alkoxy, optionally substituted Ci-Cβ-alkylthio or

R ² ; R ⁴ and R ³ ; R ^s independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,

Y stands for S0 ₂ -Y ¹ or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ ,

Y ² and Y ³ independently of one another for optionally substituted C ₁ -C ₂ alkyl, optionally substituted C ₆ -C ₁₀ aryl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical,

-OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ or Y ² and Y ³ together represent a bridge,

R ⁶ and R ⁷ independently of one another for optionally substituted C 1 -C ₂ -alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ - C ₁₂ alkenyl, optionally substituted C ₂ -C ₁₂ alkynyl, optionally substituted C ₇ -C ₂ aralkyl, optionally substituted C ₆ -C ₀ aryl or a five- or six-membered heterocyclic ring or

3. A process for the preparation of compounds of the formula (V) according to claim 22, characterized in that an m-phenylenediamine of the formula (VI)

embedded image in which

R ² and R ³ independently of one another for hydrogen, optionally substituted C 1 -C ₂ -

Alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ -C ₂ aralkyl, optionally substituted Ce or aryl are a five- or six-membered heterocyclic ring or

R ⁴ and R ⁵ independently of one another represent hydrogen, halogen, optionally substituted C ₁ -C ₆ -alkyl, optionally substituted CrC ₆ alkoxy, optionally substituted C ₁ -C ₆ alkylthio or

with a sulfuric acid or phosphoric acid derivative of the formulas

Z'-SOs-Y ¹ (VH) or

Z'-POY (m)

wherein

Z ^{1 represents} chlorine or bromine,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NRV, Y ² and Y ³ independently of one another for optionally substituted -Ci _∑ alkyl, optionally substituted C6-C ₁₀ aryl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical,

R ⁶ and R ⁷ independently of one another for optionally substituted C 1 -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C _{] 2} alkynyl, optionally substituted C ₇ - ₂ aralkyl, optionally substituted Cβ-cio-aryl or a five- or six-membered heterocyclic ring or

implements.

24. A process for the preparation of compounds of formula (V) according to claim 22, wherein.

Y stands for POY ² Y ³ , characterized in that an m-phenylenediamine of the formula (VT)

embedded image in which

R ² and R ³ independently of one another for hydrogen, optionally substituted -C ₁₂ -

Alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ -C ₂ aralkyl, optionally substituted C ₆ -Cι ₀ - Aryl or a five- or six-membered heterocyclic ring or

NR ² R together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals, R ⁴ and R ⁵ independently of one another represent hydrogen, halogen, optionally substituted C ₁ -C ₆ -alkyl, optionally substituted C ₁ -C ₆ -alkoxy, optionally substituted C ₁ -C ₆ -alkylthio or

with a phosphinic acid derivative of the formulas

HPOY ² Y ³ (IX) or

P (OH) Y ² Y ³ (X),

wherein

Y ² and Y ³ independently of one another represent -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ ,

R ⁶ and R ⁷ independently of one another for optionally substituted C 1 -C ₁₂ alkyl, optionally substituted C ₃ -Cs cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C _{] 2} alkynyl, optionally substituted tes C ₇ -C ₂ -aralkyl, optionally substituted C ₆ -Cι stand or _0-aryl or a five or six membered heterocyclic ring

in the presence of CC1 or CBrCl ₃ .

25. A process for the preparation of compounds of formula (V) according to claim 22, where Y is SO ₂ Y ¹ , characterized in that

an m-phenylenediamine of the formula (VI)

wherein

R ² and R ³ independently of one another for hydrogen, optionally substituted C ₁ -C ₁₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl, optionally substituted C ₂ -C ₂ alkyl, given - If substituted C ₇ -C ₂ aralkyl, optionally substituted Cβ-cio-aryl or a five- or six-membered heterocyclic ring or

Ci-C _ö alkyl, optionally substituted Ci-Cβ-alkoxy, optionally substituted Cι-C ₆ alkylthio or

with chlorosulfonic acid and then with Phosphoφentachlorid and this intermediate of the formula

wherein R ² to R ^{5 have} the meaning given above,

with an alcohol, phenol or amine of the formulas

HEAR ⁶ (XU),

H ₂ NR ⁶ (XTTT) or

HNR ⁶ R ⁷ (XIV), embedded image in which

C ₁₂ alkenyl, optionally substituted C ₂ -C ₂ alkynyl, optionally substituted C ₇ -C ₂ aralkyl, optionally substituted C ₆ -C aro or a five- or six-membered heterocyclic ring or

NR'T ⁷ together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,

implements.

26. Solution of metal complexes according to at least one of claims 1 to 10, characterized in that it contains at least 1% by weight of the metal complex and that the solvent is 2,2,3,3-tetrafluoropropanol, propanol, butanol, pentanol, hexanol, Diacetone alcohol, dibutyl ether, heptanone or mixtures thereof is used.

27. Solution of metal complexes according to claim 26 or 27, characterized in that propanol, butanol, pentanol, hexanol, diacetone alcohol or mixtures thereof is used as the solvent.

28. Solution of metal complexes according to claim 26, characterized in that a mixture of propanol / diacetone alcohol or butanol is used as the solvent.

29. Optical data carrier containing a preferably transparent substrate, optionally already coated with one or more reflection layers, on the surface of which an information layer which can be written on with light, optionally one or more reflection layers and optionally a protective layer or a further substrate or a covering layer, which are coated with blue or red light, preferably laser light, can be described and read, the information layer containing a light-absorbing compound and optionally a binder, characterized in that at least one metal complex according to at least one of claims 1 to 9 is used as the light-absorbing compound.

30. Optical data carrier according to claim 29, characterized in that the light-absorbing compound corresponds to the formula (Ia)

wherein the two ligands of formula (I) independently of one another have the meaning given in claim 1 and

M stands for a metal, or

of the formula (Ib)

[<»] M ⁺ Arr (Ib)

M stands for a metal and

An ^"stands for an anion.

31. Optical data carrier according to claim 30, characterized in that the metal M in formula (Ia) stands for a divalent metal, transition metal or rare earth, in particular for Mg, Ca, Sr, Ba, Cu, Ni, Co, Fe , Zn, Pd, Pt, Ru, Rh, Th, Os, Sm, Eu, and in formula (Ib) stands for a trivalent metal, transition metal or rare earth, in particular for B, Al, Ga, In, V, Co , Cr, Fe, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb.

32. Optical data carrier according to one or more of claims 29 to 31, characterized in that a metal complex is used as the high-absorption compound which has an azo ligand of the formula (I),

wherein X ^{1 represents} O, S, NR ¹ or CH,

R ^{1 represents} hydrogen, optionally substituted C 1 -C ₂ alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -C ₂ alkenyl or optionally substituted C ₇ -C ₂ aralkyl,

R ² and R ³ are independently hydrogen, optionally substituted C ₁ - ₂ - alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -Cι ₂ alkenyl optionally substituted C, ₂ -Cι ₂ alkynyl optionally substituted C ₇ -C ₂ aralkyl, optionally substituted C6-C ₁₀ aryl or a five- or six-membered heterocyclic ring or

Y stands for S0 ₂ -Y 'or POY ² Y ³ ,

Y ^{1 represents} -OR ⁶ , -NH-R ⁶ or NR ⁶ R ⁷ ,

Y ² and Y ³ independently represent optionally substituted Cι-C] ₂ alkyl, optionally substituted C ₆ -Cι ₀ aryl, an optionally substituted five- or six-membered quasi-aromatic, or aromatic heterocyclic group, -OR ^6, -NH-R ⁶ or NR ⁶ R ⁷ or Y ² and Y ³ together represent a bridge, R ⁶ and R ⁷ independently of one another for optionally substituted C ₁ -C ₂ -alkyl, optionally substituted C ₃ -C ₈ cycloalkyl, optionally substituted C ₂ -

33. A method for producing the optical data carrier according to claim 29, which is characterized in that a preferably transparent, optionally with a

Reflection layer already coated substrate with metal complexes according to claim 1 optionally coated in combination with suitable binders and additives and optionally suitable solvents and optionally provided with a reflective layer, further intermediate layers and optionally a protective layer or another substrate or a cover layer.

34. Optical data carrier according to claim 29 described with blue or red, in particular red light, in particular red laser light.