WO2005068459A1

WO2005068459A1 - Metallic complexes used as light-absorbent compounds in the information layer of optical data carriers

Info

Publication number: WO2005068459A1
Application number: PCT/EP2005/000362
Authority: WO
Inventors: Horst Berneth; Karin HASSENRÜCK; Christa-Maria KRÜGER; Josef-Walter Stawitz; Timo Meyer-Friedrichsen; Friedrich-Karl Bruder; Rafael Oser; Serguei Kostromine
Original assignee: Lanxess Deutschland Gmbh
Priority date: 2004-01-20
Filing date: 2005-01-15
Publication date: 2005-07-28
Also published as: CN1910179A; JP2007535421A; EP1709039A1; DE102004002758A1; TW200538454A

Abstract

The invention relates to optical data carriers containing a preferably transparent substrate that is optionally already coated with at least one reflective layer. An information layer on which data can be written with light, optionally at least one reflective layer, and optionally a protective layer or another substrate or a covering layer, are applied to the surface of said substrate, and can be written on or read with a blue light, preferably light having a wavelength of between 360-460 nm, especially between 390 and 420 nm, preferably between 400 and 410 nm, and preferably laser light. The information layer contains a light-absorbent compound and optionally a binding agent. The inventive data carriers are characterised in that at least one metallic complex is used as a light-absorbent compound, comprising at least one ligand of formula (I) wherein (A) represents an optionally substituted and/or benzene-annelated or naphthane-annelated, five or six-membered, aromatic or quasi-aromatic or partially hydrated, heterocyclic radical, n represents 0 or 1, Y1 represents N or C-R1, Y2 represents N or C-R2, Y3 represents N or C-R3, X represents O, S or N-R5, R5 represents hydrogen, alkyl, alkenyl, aralkyl, cycloalkyl, acyl, aryl or a heterocyclic radical, Rl to R4 independently represent hydrogen, halogen, alkyl, alkoxy, monoalkylamino or dialkylamino, aralkyl, aryl, hetaryl, arylazo, hetarylazo, cyano or alkoxycarbonyl, R1; R2, R2; R3 and R4; R5 can respectively form a bridge independently from each other, and R2; R5 can form a bridge when n is 0.

Description

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

The invention relates to optical data storage devices containing metal complexes in their information layer, a process for their production, the metal complexes contained, their production and the ligands on which the metal complexes are based and processes for their production.

The write-once optical data carriers using special light-absorbing substances or mixtures thereof are particularly suitable for use in high-density writable optical data memories that work with blue laser diodes, in particular GaN or SHG laser diodes (360 - 460 nm).

The compact disk (CD-R, 780 nm), which can be written on once, has recently seen enormous 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 DVD-R (DVD-R, 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 memories which are equally suitable for CD-R and DVD-R systems (JP-A 11 043 481 and JP-A 10 181 206). For a high reflectivity and a high modulation level of the readout signal, as well as for a sufficient sensitivity when writing, use is made of 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 one Wavelength 635 nm or 650 nm of the DVD-R lies at the foot of the short-wave flank of the absorption peak of the dye. This concept is described, for example, in WO-A 09 917 284 and US-A 5 266 699 in the 450 nm range. line length extended on the short-wave flank and the red and IR areas on the long-wave flank of the absorption peak.

Dyes for the blue laser are also known from WO-A 03/063151.

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 a vacuum is prevented.

The amorphous layer of light-absorbing substances should preferably have a high heat resistance, since otherwise further layers of organic or inorganic material, which are applied to the light-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 insufficient heat resistance at the interface to a polymer carrier can diffuse into the latter 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 data carriers equipped with suitable connections which meet the high requirements (such as light stability, favorable signal-to-noise ratio, damage-free application to the substrate material, etc.) for use in the formation layer in a write-once optical data carrier for fulfill high-density writable optical data storage formats in a laser wavelength range from 360 to 460 nm. The numerical aperture NA of the objective lens is preferably greater than or equal to 0.60, particularly preferably greater than or equal to 0.70, very particularly preferably greater than or equal to 0.80.

It has surprisingly been found that optical data carriers with light-absorbing compounds from the group of special metal complexes can meet the above-mentioned requirement profile particularly well. The invention therefore relates to optical data carriers containing a preferably transparent substrate, optionally already coated with one or more reflection layers and / or protective layers, on the surface of which an information layer which can be written on by light - optionally one or more reflection layers and optionally a protective layer or another substrate or one Cover layer are applied, which can be written and read with blue light, preferably with a wavelength in the range of 360-460 nm, in particular 390 to 420 nm, very particularly preferably from 400 to 410 nm, preferably laser light, the information layer being a contains light-absorbing compound and optionally a binder, characterized in that at least one metal complex is used as the light-absorbing compound, which has at least one ligand of formula (I)

wherein

the rest of the formula (hereinafter referred to as A)

represents an optionally substituted and / or benzyl- or naphthane-fused five- or six-membered aromatic or quasi-aromatic or partially hydrogenated heterocyclic radical,

n represents 0 or 1,

Y ^{1 represents} N or CR ¹ ,

Y ^{2 stands} for N or CR ", stands for N or CR ³ ,

X represents O, S or NR ⁵ ,

R ⁵ is hydrogen, alkyl, alkenyl, aralkyl, cycloalkyl, acyl, aryl or a hetero ^¬ cychschen residue provides, R ^ is R independently of one another are hydrogen, halogen, alkyl, alkoxy, mono- or dialkylamino, aralkyl, aryl, hetaryl, arylazo, hetarylazo, cyano or alkoxycarbonyl,

R *; R ^{2 can form} an optionally substituted and / or optionally containing heteroatoms triatomic bridge or an optionally substituted fouratoms bridge which contains no or at least 2 heteroatoms, in particular R * and R ² together represent an optionally substituted bridge with the atomic sequence - CR-N-NR "-, - (CO) -NR" - (CO) -NR '", - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ - or -CH = CH-CH = CH-, where R 'to R'"independently of one another are hydrogen, alkyl, in particular C ₁ -C 4 -alkyl or aryl, in particular Cg-C 1 _Q- aryl, preferably H, methyl or phenyl,

R ² ; R ³ and R; R ⁵ can each independently form an optionally substituted bridge and

R ² ; R ⁵ can form an optionally substituted bridge if n is 0.

N is preferably 0. Likewise, n is preferably 1.

Although of course, it should be mentioned for the sake of completeness that ligands of the formula (I) also mean the corresponding tautomers, e.g. B. those of the formula (! ')

wherein the radicals have the meaning given above.

In a preferred embodiment, the rest of the formula

for -N = N-, -CR ^J = N-, -CR '= CR ² -, ~ N = CR ² -, -CR ¹ = NN = CR ⁴ -, -N = NN = CR ⁴ -, -CR ¹ = CR ² -N = CR ⁴ - or -CR ¹ = CR ² -CR ³ = CR ⁴ -, particularly preferably for -N = N-, -CR ^{1 =} N-, -CR ^ CR ² -, -N = CR ² -, -N = NN = CR ⁴ -, -CR ¹ = CR ² -N = CR ⁴ - or -CR ¹ = CR ² -CR ³ = CR ⁴ -,

wherein R ¹ to R ^{4 have} the meaning given above. X is preferably NR ⁵ , where R ^{5 has} the meaning given above.

R ² and R ⁵ likewise preferably form a bridge in the case of n = 0 or R ⁴ and R ⁵ in the case of n = 1. Then particularly preferably -CR ² -N ^Θ -R ⁵ or -CR ⁴ -N ° -R ^{5 stands} for a ring of the formula (X)

wherein the rest of the formula (X) as a protonated tautomer of the formula

is briefly referred to as B and

in which B represents an optionally substituted and / or benzyl or naphthane-fused five- or six-membered aromatic or quasi-aromatic or partially hydrogenated heterocyclic radical.

In a preferred embodiment, the metal complexes are in the form of 1: 1, 1: 2 or 1 ^ metal complexes.

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

Preferred metal complexes are those which are characterized in that they have the formula (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.

Preferred metal complexes are those which are characterized in that they have the formula (Ib)

[(I)] »M * ^{/ + ■} A .n- C ^&) correspond in which the ligand of formula (I) has the meaning given above,

M stands for a metal and

An ^"stands for an anion.

Preferred metals of the metal complexes used according to the invention are:

Mg, Ca, Sr, Ba, Cu, Ni, Co, Fe, Zn, Pd, Pt, Ru, Th, Os, Sm, B, AI, Ga, In, V, Cr, Y, La, Ce, Pr, Nd, En, Gd or Tb.

Preferred metals in formulas (la) and (Ib) are divalent metals, transition metals or rare earths, in particular Mg, Ca, Sr, Ba, Cu, Ni, Co, Fe, Zn, Pd, Pt, Ru, Th, Os or sm in question. The metals Pd, Fe, Zn, Cu, Ni and Co. are preferred. Ni is particularly preferred.

Also preferred are those metal complexes which are characterized in that they have the formula (Ic)

[<->] M ⁺ An (Ic)

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

M stands for a metal and

An ^"stands for an anion.

Preferred metals in the formula (Ic) are trivalent metals, transition metals or rare earths, in particular B, Al, Ga, In, V, Co, Cr, Fe, Y, La, Ce, Pr, Nd, Sm, Eu, Gd or Tb in question. B, Al and Co. are preferred. Co. is particularly preferred.

Statistical mixtures of metal complexes which are characterized in that they contain two different ligands of the formula (I) are also preferred.

A is preferably 2-pyridyl, 2-quinolyl, 2-pyrimidyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,3-thiazol-2-yl, 1,3-thiazolin 2-yl, l, 3-thiazol-4-yl, benzothiazol-2-yl, l, 2-thiazol-3-yl, benzoisothiazol-3-yl, l, 3-oxazol-2-yl, l, 3-oxazolin-2-yl, benzoxazol-2-yl, 1,2-oxazol-3-yl, imidazol-2-yl,

Imidazolin-2-yl, benzimidazol-2-yl, imidazol-4-yl, pyrazol-5-yl, pyrrolin-2-yl, pyrrol-2-yl, 1,3,4- Triazol-2-yl, 3H-indolin-2-yl, tetrahydroisoindol-l-yl, isoindol-l-yl, benz (cd) indol-2-yl, 1,3,4-thiadiazol-2-yl, l, 2,4-thiadiazol-5-yl, l, 2,4-thiadiazol-3-yl or l, 3,4-oxadiazol-2-yl, which may optionally be substituted.

A is particularly preferably 2-pyridyl, 2-quinolyl, 1,3-thiazol-2-yl, 1,3-thiazolin-2-yl, benzothiazol-2-yl, 1,3-oxazol-2-yl, benzoxazole -2-yl, imidazol-2-yl, benzimidazol-2-yl, pyrazol-5-yl, pyrrolin-2-yl, pyrrol-2-yl, l, 3,4-triazol-2-yl, 3H-indoline -2-yl, tetrahydroisoindol-l-yl, isoindol-l-yl, benz (cd) indol-2-yl, l, 3,4-thiadiazol-2-yl, l, 2,4-thiadiazol-5-yl or 1,3,4-oxadiazol-2-yl, which may optionally be substituted.

Suitable substituents for A are, for example, C ₁ -C ₁₂ alkyl, CrCπ alkoxy, fluorine, chlorine, bromine, iodine, hydroxy, oxo, cyano, -C (= NH) -OC C ₆ alkyl, nitro, carboxy, CC ₆ -alkoxycarbonyl, mono- or di-Ci-Cö-alkylaminocarbonyl, -C-C ₆ -alkylthio, Cι-C ₆ -acylamino, - - alkylsulfonylamino, C _ß -Cio-arylsulfonylamino, formyl, C ₂ -C ₆ - Alkanoyl, sulfo, mono- or di-C ₆ -C ₆ -alkylaminosulfonyl, Ce-Cio-aryl, C ₆ -cio-aryloxy, C ₆ -C 8 -arylcarbonylamino, mono- or di-Cx-C _δ -Al ylamino, NC Ce -Alkyl-NC _ö -Cio-arylamino, pyrrolidino, morpholino, piperazino or piperidino, which in turn can optionally be substituted.

Substituents from the series of the branched C ₃ -C ₈ alkoxy radicals are particularly preferred, for example -O-CH ₂ -CH (CH ₃ ) ₂ , -O-CH [CH (CH ₃ ) ₂ ] ₂ , -OC (CH ₃ ) ₃ , -O-CH ₂ -CH (C ₂ H ₅ ) (C ₄ H ₉ ), -O-CH ₂ -C (CH ₃ ) ₂ -C ₂ H ₅ , the branched or ring-closed C2-C ₃ - Alkylaminomethyl radicals, for example -CH ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -CH ₂ NH-CH ₂ -CH (C ₂ H ₅ ) (C ₄ H ₉ ), -CH ₂ NH-CH [CH ( CH ₃ ) ₂ ] ₂ , a radical of the formula

the optionally branched C ₂ -C ₅ alkoxycarbonyl radicals, for example -COOCHjCTL _j , -COO-CH (CH ₃ ) ₂ , -COO-CH [CH (CH ₃ ) ₂ ] 2, the optionally branched or ring-closed C2-Cg-alkylaminosulfonyl radicals , for example -SO ₂ N (CH ₂ CH (CH3)) ₂ , -S0 ₂ NHCH ₂ CH (CH ₃ ) ₂ , -SO ₂ NHC (CH ₃ ) ₂ CH ₂ CH ₃ , -SO ₂ NHC (CH ₃ ) ₃ ,

-S0 ₂ NH- (CH ₂ CH ₂ CH ₂ O-) 2CH3, -SO ₂ NH- (CH ₂ CH ₂ CH ₂ 0) - (CH ₂ CH ₂ O) -CH ₃ ,

-S0 ₂ N (CH ₂ CHOH) ₂ , SO ₂ N (CH ₂ CH (CH ₃ ) CH ₂ OH) ₂ and / or a radical of the formula

Likewise suitable substituents of A are in particular in the case of A = 2-pyridyl, 1,3,4-triazol-2-yl, l, 3,4-thiadiazol-2-yl or l, 3,4-oxadiazol-2- yl is a radical of the formula (XI)

wherein Y ¹ to Y ³ , R ⁴ , n and X have the meaning given above.

Likewise suitable substituents of A are in particular in the case of A = pyrrole-2yl in position 5 and in the case of A = tetrahydroisoindol-l-yl or isoindol-1-yl in position 3 the radical = O, = S or a radical of the formulas (Xu) to (XIV)

R ° CN (Xm) or ^κ (XIV)

wherein Y ¹ to Y ³ , R ⁴ , n and X have the meaning given above, but are independent thereof

R ^{6 represents} hydrogen, Cx-C _ό alkyl or C ₆ -Cι ₀ aryl and

R ^{7 represents} hydrogen, Ci-Cβ-alkyl, C ₆ -C ₁₀ aryl or a heterocyclic radical.

In the formulas (XI) and (XU), the radical X preferably represents NR ⁵ , where R ^{5 has} the meaning given above.

A very preferably stands for

2-pyridyl, which contains up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, tert-butoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, tert pentylaminosulfonyl, bis (hydroxyethyl) aminosulfonyl, morpholinosulfonyl, methoxyethoxypropylaminosulfonyl, nitro or cyano may be substituted, 2-Quinolyl, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, tert-butoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, tert. pentylaminosulfonyl, bis (hydroxyethyl) aminosulfonyl, morpholinosulfonyl, methoxyethoxypropylaminosulfonyl, nitro or cyano may be substituted,

l, 3-thiazol-2-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methoxy, phenyl or cyano,

Benzthiazol-2-yl, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, tert-butoxy, 2,4-dimethyl-3-pentoxy, methoxycarbonyl, di-isobutylamino -sulfonyl, tert-pentylaminosulfonyl, bis- (hydroxyethyl) aminosulfonyl, morpholinosulfonyl, methoxyethoxypropylaminosulfonyl, nitro or cyano may be substituted,

Benzoxazol-2-yl, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, tert-butoxy, 2,4-dimethyl-3-pentoxy, methoxycarbonyl, di-isobutylamino sulfonyl, tert-pentylaminosulfonyl, bis- (hydroxyethyl) aminosulfonyl, morpholinosulfonyl, methoxyethoxypropylaminosulfonyl, nitro or cyano may be substituted,

Imidazol-2-yl, which can be substituted by up to two identical or different radicals from the series chlorine, methyl, methoxy, phenyl, cyano, -C (= NH) -OCH ₃ , nitro, methoxycarbonyl or ethoxycarbonyl,

Benzimidazol-2-yl, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, tert-butoxy, 2,4-dimethyl-3-pentoxy, methoxycarbonyl, di-isobutylamino -sulfonyl, tert-pentylaminosulfonyl, bis- (hydroxyethyl) aminosulfonyl, Mo holinosulfonyl, methoxyethoxypropylaminosulfonyl, nitro or cyano may be substituted,

l, 3,4-thiadiazol-2-yL 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 may be substituted,

Pyrrol-2-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano and / or the in

Position 3,4 carries a - {CTLJr or - (CH ₂ ) bridge and / or that in position 5 by hnino, Dicyanomethylene, methoxycarbonyl-cyano-methylene, ethoxycarbonyl-cyano-methylene or a radical of the formula (XU)

in which X is NR ⁵ and Y ¹ to Y ³ , R ⁴ , n and R ^{5 have} the meaning given above, but are independent thereof, and can be substituted,

3-HTndolin-2-yl, which bears two methyl groups or an oxo group in position 3 and can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano,

Isoindol-1-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano and / or which is in position 3 by imino, dicyanomethylene, methoxycarbonyl-cyano- methylene, ethoxycarbonyl-cyano-methylene or a radical of the formula (XU)

wherein X is NR ⁵ and Y ¹ to Y ³ , R ⁴ , n and R ^{5 have} the meaning given above but are independent of it, can be substituted or

l, 2,4-triazol-2-yl, which can be substituted by methyl or phenyl.

B as the basic structure on which the formula X is based preferably has the same meaning as A, the meanings A and B being independent of one another.

However, B is particularly preferably not substituted by a radical of the formula (XI) or (XII).

For example, with B = 2-pyridyl is a radical of the formula (Xa)

meant. The same procedure is followed with the other heterocycles listed. The metal complexes used according to the invention which have at least one ligand of the formulas (IA) to (I-ZA) are particularly preferred

worm

A and B 'independently of one another for 2-pyridyl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, nitro or cyano,

2-quinolyl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, nitro or cyano, l, 3-thiazol-2-yl, by up to two identical or different radicals can be substituted from the series chlorine, fluorine, methoxy, phenyl or cyano,

Benzthiazol-2-yl, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, diisobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano may be substituted

Benzoxazol-2-yl, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, diisobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano may be substituted

Imidazol-2-yl, which can be substituted by up to two identical or different radicals from the series chlorine, methyl, methoxy, phenyl, cyano, -C (= NH) -OCH ₃ , nitro, methoxycarbonyl or ethoxycarbonyl, benzimidazole-2 -yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, diisobutylaminosulfonyl, methoxycarbonyl, nitro or cyano can l, 3,4-thiadiazol-2-yl, which by chlorine, bromine, methoxy, phenoxy, methanesulfonyl, methylthio, ethylthio, dimethylamino, diethylamino, di- (iso) -propylamino,] -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,

3-H-indolin-2-yl which bears two methyl groups or an oxo group in position 3 and can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano .

Isoindol-1-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano and / or which is in position 3 by imino, dicyanomethylene, methoxycarbonyl-cyano- methylene, ethoxycarbonyl-cyano-methylene may be substituted, or 1,2,4-triazol-2-yl, which may be substituted by methyl or phenyl,

A 'for pyridin-2-yl-6-ylidene, l, 3,4-triazol-2yl-5-ylidene, pyrrol-2yl-5-ylidene, 3,4-tetra-methylenepyrrol-2yl-5-ylidene or optionally isoindolyl-3-ylidene which is substituted by fluorine, chlorine, methyl, methoxy, methoxycarbonyl, nitro or cyano,

B for pyridin-2-ylidene, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, nitro or cyano,

Quinolin-2-ylidene, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, nitro or cyano, l, 3-thiazol-2-ylidene, which can be substituted by up to two identical or various residues from the series chlorine, fluorine, methoxy, phenyl or cyano can be substituted,

Benzthiazol-2-ylidene, which is composed of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, Nitro or cyano can be substituted,

Benzoxazol-2-ylidene, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano may be substituted Imidazol-2-ylidene, which can be substituted by up to two identical or different radicals from the series chlorine, methyl, methoxy, phenyl, cyano, -C (= NH) -OCH ₃ , nitro, methoxycarbonyl or ethoxycarbonyl,

Benzimidazol-2-ylidene, which is formed by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, diisobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano may be substituted, l, 3,4-thiadiazol-2-ylidene by chlorine, bromine, methoxy, phenoxy, methanesulfonyl, methylthio, ethylthio, dimethylamino, diethylamino, di- (iso) propylamino, N-methyl-N Cyanoethylamino, N, N-biscyanetyllylamino, N-methyl-N-hydroxyethylamino, N-methyl-N-benzylamino, N-methyl-N-phenylamino, anilino, pyrrolidino, piperidino or Moφholino can be substituted,

Isoindol-1-ylidene, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano and / or which is in position 3 by imino, dicyanomethylene, methoxycarbonyl-cyano- methylene, ethoxycarbonyl-cyano-methylene can be substituted, or 1,2,4-triazol-2-ylidene which can be substituted by methyl or phenyl,

R ¹ to R ⁴ independently of one another represent hydrogen, chlorine, methyl, benzyl, pyridylmethyl, phenyl, cyano, methoxycarbonyl or ethoxycarbonyl and

R ² additionally represents methoxy, ethoxy, dimethylamino, diethylamino, pyrrolidino or piperidino, or

R ^ R ² in formula (IH), (IJ), (IO), (IP), (IU) to (I-ZA) together for a bridge optionally substituted by methyl, phenyl and / or cyano with the atomic sequence -CR '= N-NR "-, - (C = O) -NR" - (C = O) -NR "' -, where R 'to R'" have the meaning given above, or

R *; R ² in formula (IE), (IF), (IH), (IJ), (IO), (IP), (IU) to (I-ZA) together for one - (CH ₂ ) ₃ - , - (CH ₂ ) ₄ - or -CH = CH-CH = CH-bridge and

R ^{5 is} methyl, ethyl, phenyl-, 2-, 3- or 4-pyridyl-, 2-, optionally substituted by up to two identical or different radicals from the series methyl, methoxy, chlorine, nitro, cyano, methylsulfonyl, methoxycarbonyl, ethoxycarbonyl , 3- or 4-quinolyl-, thiazol-2-yl-, benzthiazol-2-yl-, benzoxazol-2-yl-, imidazol-2-yl-, benzimidazol-2-yl-, l, 3,4- triazole-2- yl radicals, formyl, acetyl, trifluoroacetyl, acryloyl, methacryloyl, benzoyl, methylbenzoyl, chlorobenzoyl, methanesulfonyl, trifluoromethanesulfonyl, perfluorobutanesulfonyl, benzenesulfonyl, toluenesulfonyl, chlorobenzenesulfonyl, dimethylnoxylamyll, methoxyethylamyllamoyl, methoxyethylamyllamyloxy, methylcarbonylamoyl, methoxyethylamyllamyloxy, methylcarbonylamoyl, methoxyethylamyllamyloxy, methoxyethylamyllamyl, methoxyethylamyllamyloxy, methoxyethylamyllamyloxy, methylcarbonylamyl, methoxyethylamyllamyl, methoxyethylamyl, methoxy nyl, methoxy methylamyl, methyl carbonyl, methoxy nyl, methoxy nyl, methoxy methylamyl, methoxy nyl, methoxy nyl, methoxy methylamyl, methoxy nyl, methoxy nyl, methoxy nyl, methoxy nyl, methoxy nyl, methoxy nyl, methoxy methyl amyl, methoxy nyl, N-2,2,2-trifluoroethylsulfamoyl, N-methyl-N-2,2,2-trifluoroethylsulfamoyl, pyridine-2-, 3- or 4-carbonyl, pyridine-2-, 3- or 4-sulfonyl or Benzothiazole-2-sulfonyl,

Y ⁴ for = 0, = S or a remainder of the formulas

R ^β (XΠΓ) or ΠM

^ R ⁷ (XIV) stands,

R ^{6 represents} hydrogen, phenyl, cyano, methoxycarbonyl or ethoxycarbonyl

and

R ^{7 represents} hydrogen, methyl, ethyl, phenyl, tolyl, chlorophenyl, anisyl, 2-pyridyl, thiazol-2-yl or benzthiazol-2-yl,

wherein each of the formulas (I-A) to (I-ZA) is particularly preferred in itself.

The formulas (IA) to (IC), (IG), (IH), (IJ) to (IL), (IO), (IQ), (IR), (IU), (I-W) and (IX).

The formulas (I-A) and (I-B) are particularly preferred,

wherein

R ^{1 represents} hydrogen, benzyl, phenyl, cyano methoxycarbonyl or ethoxycarbonyl,

A represents a 2-pyridyl, l, 3-thiazol-2-yl, benzothiazol-2-yl or benzoxazol-2-yl radical which is represented by -0-CH ₂ -CH (CH ₃ ) ₂ , -O-CH [CH (CH ₃ ) ₂ ] ₂ , -OC (CH ₃ ) ₃ , -O-CH ₂ -CH (C ₂ H5) (C ₄ H ₉ ), -O-CH ₂ -C (CH ₃ ) ₂ -C ₂ H ₅ , -SO ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -COOCH ₂ CH ₃ , -S0 ₂ NHCH ₂ CH (CH ₃ ) ₂ , -SO ₂ NHC (CH ₃ ) ₂ CH ₂ CH ₃ , -SO ₂ NHC (CH ₃ ) ₃ , -CH ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -SO ₂ NH- (CH ₂ CH ₂ CH ₂ 0-) ₂ CH ₃ , -SO ₂ NH- (CH ₂ CH ₂ CH ₂ O) - (CH ₂ CH ₂ 0) -CH ₃ , -SO ₂ N (CH ₂ CHOH) ₂ , SO ₂ N (CH ₂ CH (CH ₃ ) CH ₂ OH) _2;

and / or is substituted,

B represents a pyridin-2-ylidene, 1,3-thiazol-2-ylidene, benzothiazol-2-ylidene or benzoxazolidene-2-yl radical which is replaced by hydrogen, -O-CH ₂ -CH (CH ₃ ) ₂ , -O-CH [CH (CH ₃ ) ₂ ] ₂ , -OC (CH ₃ ) ₃ , -O-CH ₂ -CH (C ₂ H ₅ ) (C ₄ H ₉ ), -O -CH ₂ -C (CH ₃ ) ₂ -C ₂ H ₅ , -SO ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -COOCH ₂ CH ₃ , -SO ₂ NHCH ₂ CH (CH ₃ ) ₂ , -SO ₂ NHC (CH ₃ ) ₂ CH ₂ CH ₃ , -SO ₂ NHC (CH ₃ ) ₃ , -CH ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -S0 ₂ NH- (CH ₂ CH ₂ CH ₂ O-) ₂ CH ₃ , -SO ₂ NH- (CH ₂ CH ₂ CH ₂ O) - (CH ₂ CH ₂ 0) -CH ₃ , -S0 ₂ N (CH ₂ CHOH) ₂ , SO ₂ N ( CH ₂ CH (CH ₃ ) CH ₂ OH) _2j

and / or is substituted.

In formulas (I-A) and (I-B), rings A and B are very particularly preferably identical.

Formula (I-C) is particularly preferred

wherein

R ^{1 represents} hydrogen, benzyl, phenyl, cyano, methoxycarbonyl or ethoxycarbonyl,

A represents a 2-pyridyl, 2-quinolyl or 3,3-dimethylindolin-2-yl radical which can be substituted by methyl, methoxy, chlorine or methoxycarbonyl,

B for a pyridin-2-ylidene, 1,3-thiazol-2-ylidene or benzothiazol-2-ylidene residue which can be substituted by chlorine, methyl, methoxy, cyano or methoxycarbonyl, 1,3,4- Thiadiazol-2-ylidene radical, which may be substituted by methylthio, dimethylamino, diethylamino, diisopropylamino, pyrrolidino or morpholino, or 1,3,4-triazol-2-ylidene radical.

The formula (I-C) is very particularly preferred

wherein R ^{1 represents} hydrogen or cyano,

A represents a 2-pyridyl, 2-quinolyl or 3,3-dimethylindolin-2-yl radical,

B is a 1,3-thiazol-2-ylidene or benzothiazol-2-ylidene radical, 1,3-thiadiazol-2-ylidene radical which may be substituted by dimethylamino, diethylamino, diisopropylamino, pyrrolidino or morpholino , or l, 3,4-triazol-2-ylidene radical.

The formulas (I-G), (I-H) and (I-J) are particularly preferred.

wherein

R ^{1 represents} hydrogen, phenyl or cyano,

R ^{2 represents} hydrogen or

R *; R ² stand for a -CH = CH-CH = CH bridge,

R ^{5 is} phenyl, tolyl, chorphenyl, nitrophenyl, 2-, 3- or 4-pyridyl, thiazol-2-yl, benzothiazol-2-yl, trifluoroacetyl, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, cyanobenzenesulfonyl, N, N-dimethylsulfamyl , Pyridine-2-, 3- or 4-sulfonyl,

A represents a 2-pyridyl, 2-quinolyl or 3,3-dimethylindolin-2-yl radical which can be substituted by methyl, methoxy, chlorine or methoxycarbonyl.

The formula (I-G) is very particularly preferred,

wherein

R ^{1 represents} hydrogen,

R ^{5 represents} phenyl, tolyl, chorphenyl, nitrophenyl, 2-, 3- or 4-pyridyl, thiazol-2-yl or benzthiazol-2-yl,

The formulas (I-H) and (I-J) are also very particularly preferred,

wherein

R *; R ² stand for a -CH = CH-CH = CH bridge, R ^{5 is} trifluoroacetyl, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, cyanobenzenesulfonyl, N, N-dimethylsulfamoyl, pyridine-2-, 3- or 4-sulfonyl,

The formulas (I-K) and (I-Q) are particularly preferred,

wherein

Y ^{4 stands} for = 0, = S, = NH or = C (CN) ₂ ,

A 'for 3,4-tetramethylene-pyrrol-2-yl-5-ylidene, a pyrrol-2-yl-5-ylidene or isoindol-1-yl-3-ylidene residue, which is represented by methyl, methoxy, nitro or cyano can be substituted,

B 'represents a 2-pyridyl, 2-quinolyl, 1,3-thiazol-2yl, benzthiazol-2-yl, benzoxazol-2-yl or 3,3-dimethylindolin-2-yl radical, which can be substituted by methyl, methoxy, chlorine, cyano or methoxycarbonyl,

B for a pyridin-2-ylidene, quinolin-2-ylidene, 1,3-thiazol-2ylidene, benzothiazol-2-ylidene, benzoxazol-2-ylidene or 3,3-dimethylindolin-2-ylidene Radical which can be substituted by methyl, methoxy, chlorine, cyano or methoxycarbonyl.

The formulas (I-K) and (I-Q) are very particularly preferred,

wherein

R ^{1 represents} hydrogen or cyano,

Y ^{4 stands} for = O, = S, = NH or = C (CN) ₂ ,

A 'represents a pyrrol-2-yl-5-ylidene or isoindol-1-yl-3-ylidene radical which may be substituted by methyl or methoxy,

B 'represents a 2-pyridyl, l, 3-thiazol-2yl, benzthiazol-2-yl, benzoxazol-2-yl or 3,3-dimethylindolin-2-yl radical, which is represented by methyl, methoxy , Cyano or methoxycarbonyl may be substituted, B represents a pyridin-2-ylidene, 1,3-thiazol-2ylidene, benzothiazol-2-ylidene, benzoxazol-2-ylidene or 3,3-dimethylindolin-2-ylidene radical which is represented by methyl, Methoxy, cyano or methoxycarbonyl can be substituted, and

B and B 'are derived from the same heterocycle.

The formulas (I-L) and (I-R) are particularly preferred,

wherein

Y ^{4 stands} for = O, = S, = NH or = C (CN) ₂ ,

B 'for a 2-pyridyl, 2-pyrimidyl, l, 3-thiazol-2yl, benzthiazol-2-yl, benzoxazol-2-yl radical which is substituted by methyl, methoxy, chlorine, cyano or methoxycarbonyl can be l, 3,4-triazol-2-yl or a l, 3,4-thiadiazol-2-yl radical which can be substituted by dimethylamino, diethylamino, diisopropylamino, pyrrolidino or morpholino,

B for a pyridin-2-ylidene, pyrimidin-2-ylidene, l, 3-thiazol-2ylidene, benzothiazol-2-ylidene, benzoxazol-2-ylidene residue, which is characterized by methyl, methoxy, chlorine, cyano or may be substituted by methoxycarbonyl, l, 3,4-triazol-2-ylidene or a 1,3,4-thiadiazol-2-ylidene radical which may be substituted by dimethylamino, diethylamino, diisopropylamino, pyrrolidino or morpholino.

The formulas (I-L) and (I-R) are very particularly preferred,

wherein

Y ^{4 stands} for = 0, = S, = NH or = C (CN) ₂ ,

B 'for a 2-pyridyl, 2-pyrimidyl, l, 3-thiazol-2yl, benzthiazol-2-yl, benzoxazol-2-yl radical which can be substituted by methyl, methoxy or cyano, l , 3,4-triazol-2-yl or a l, 3,4-thiadiazol-2-yl radical which may be substituted by dimethylamino or diisopropylamino, B for a pyridin-2-ylidene, pyrimidin-2-ylidene, 1,3-thiazol-2ylidene, benzothiazol-2-ylidene, benzoxazol-2-ylidene residue which may be substituted by methyl, methoxy or cyano can, l, 3,4-triazol-2-ylidene or a l, 3,4-thiadiazol-2-ylidene radical, which may be substituted by dimethylamino or diisopropylamino, and

B and B 'are derived from the same heterocycle.

The formulas (I-O) and (I-U) are particularly preferred,

wherein

Y ^{4 stands} for = 0, = S, = NH or = C (CN) ₂ ,

R ^{1 represents} hydrogen,

R ^{2 represents} methoxy, ethoxy, dimethylamino, diethylamino, pyrrolidino or piperidino or

R ^J ; R ² stand for a -CH = CH-CH = CH bridge.

The formulas (I-O) and (I-U) are very particularly preferred,

wherein

Y ^{4 stands} for = 0, = S, = NH or = C (CN) ₂ ,

R ^{1 represents} hydrogen,

R ^{2 represents} dimethylamino, diethylamino, pyrrolidino or piperidino or

R *; R ² stand for a -CH = CH-CH = CH bridge.

The formula (I-W) is particularly preferred

wherein A 'for 3,4-tetramethylene-pyrrol-2-yl-5-ylidene, a pyrrol-2-yl-5-ylidene or isoindol-1-yl-3-ylidene residue, which is represented by methyl, methoxy, nitro or cyano can be substituted,

R ^{1 represents} hydrogen or cyano,

R ^{2 represents} methoxy, ethoxy, dimethylamino, diethylamino, pyrrolidino or piperidino,

B for a pyridin-2-ylidene, quinolin-2-yldenene, 1,3-thiazol-2ylidene, benzothiazol-2-ylidene, benzoxazol-2-ylidene or 3,3-dimethylindolin-2-ylidene Radical which can be substituted by methyl, methoxy, chlorine, cyano or methoxycarbonyl.

The formula (I-W) is very particularly preferred,

wherein

R ^{1 represents} hydrogen or cyano,

R ^{2 represents} dimethylamino, diethylamino, pyrrolidino or piperidino,

B represents a pyridin-2-ylidene, 1,3-thiazole ~ 2ylidene, benzothiazol-2-ylidene, benzoxazol-2-ylidene or 3,3-dimethylindolin-2-ylidene residue which is represented by methyl, Methoxy, cyano or methoxycarbonyl can be substituted.

The formula (I-X) is particularly preferred

wherein

A 'for 3, 4-tetramethylene-pyrrol-2-yl-5-ylidene, a pyrrol-2-yl-5-ylidene or isoindol-1-yl-3-ylidene residue, which is represented by methyl, methoxy, nitro or cyano can be substituted,

R ^{1 represents} hydrogen or cyano,

B for a pyridin-2-ylidene, pyrimidin-2-ylidene, l, 3-thiazol-2ylidene, benzothiazol-2-ylidene, benzoxazol-2-ylidene residue, which is characterized by methyl, methoxy, chlorine, cyano or may be substituted by methoxycarbonyl, l, 3,4-triazol-2-ylidene or a 1,3,4-thiadiazol-2-ylidene radical which may be substituted by dimethylamino, diethylamino, diisopropylamino, pyrrolidino or morpholino. Formula (IX) is very particularly preferred

wherein

R ^{1 represents} hydrogen or cyano,

R ^{2 represents} dimethylamino, diethylamino, pyrrolidino or piperidino,

B for a pyridin-2-ylidene, pyrimidin-2-ylidene, 1,3-thiazol-2ylidene, benzothiazol-2-ylidene, benzoxazol-2-ylidene residue which may be substituted by methyl, methoxy or cyano may be l, 3,4-triazol-2-ylidene or a l, 3,4-thiadiazol-2-ylidene radical, which may be substituted by dimethylamino or diisopropylamino.

Possible substituents of the alkyl, alkenyl or aralkyl radicals in the context of this application are preferably halogen, in particular Cl or F, mono- or dialkylamino radicals, pyrrolidino, morpholino, piperidino, nitro, cyano, CO-NH2, alkoxy, trialkylsilyl or Trialkylsiloxy in 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 or neopentyl.

Preferred optionally substituted C1-C12-alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl, 2-ethyl-hexyl, 2 , 4-dimethyl-3-pentyl, 2,2-dimethyl-butyl, trifluoromethyl, perfluorinated ethyl, 2,2-difluoroethyl, 3,3,3-trifluoroethyl, perfluorobutyl, cyanoethyl, methoxyethyl, chloroethyl, bis-isobutylamino, bis- tert-pentylamino, morpholino. Particularly preferred optionally substituted Ci-Cg-alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, h-hexyl,, cyanoethyl, methoxyethyl or chloroethyl. These alkyl residues are also contained in the preferred optionally substituted C 1 -C 2 -alkoxy residues.

In the context of this application, preferred aralkyl is preferably, for example, benzyl, phenethyl or phenylpropyl.

Allyl or 2-buten-1-yl is an example of a preferred alkenyl.

Preferred heterocyclic radicals or hetaryl radicals are pyridyl, thiazolyl, benzthiazolyl. Among acyl groups are preferably formyl, C ₂ -C ₆ alkanoyl, C ₃ -C ₆ alkenoyl, C ₆ -C ₁₀ aroyl, CC _ö -alkylsulfonyl, C ₆ -arylsulfonyl -Cι _0, C Cβ-alkoxycarbonyl, mono- or to understand C ₁ -C ₆ alkylamino carbonyl, mono- or di C ₁ -C ₆ alkylamino sulfonyl or a heterocyclic radical attached via a CO or S0 ₂ group, which in turn can be optionally substituted. Examples are formyl, acetyl, trifluoroacetyl, acryloyl, methacryloyl, benzoyl, methylbenzoyl, chlorobenzoyl, methanesulfonyl, trifluoromethanesulfonyl, perfluorobutanesulfonyl, benzene sulfonyl, toluenesulfonyl, chlorobenzenesulfonyl, methoxycarbonyl, ethoxycarbonyl, dimethyl- carbamoyl, dimethylsulfamoyl, pyridin-2-, 3- or 4-carbonyl, pyridine-2-, 3- or 4-sulfonyl, benzothiazole-2-sulfonyl, pyrimidine-2-sulfonyl, -S0 ₂ N (CH2CH (CH ₃ ) 2) _2J -COOCH ₂ CH ₃ , -S0 ₂ NHCH ₂ CH (CH ₃ ) ₂ , -Sθ2NHC. (CH ₃ ) 2CH ₂ CH ₃ , -S0 ₂ NHC (CH ₃ ) ₃ , -CH ₂ N (CH ₂ CH (CH ₃ ) 2) 2, -S0 ₂ NH- (CH ₂ CH ₂ CH ₂ 0-) ₂ CH ₃ , -S0 ₂ NH- (CH ₂ CH2CH2θ) - (CH ₂ CH ₂ 0) -CH3,

-S0 ₂ N (CH ₂ CHOH) ₂ , Sθ2N (CH ₂ CH (CH3) CH2θH) 2

The particularly preferred metal complexes of the formula (Ia) with ligands of the formulas (IA) to (IJ) and (IQ) to (IN) each have 2 ligands as they have a tautomeric form of the formulas (ILA) to (JT-K) and (JT-Q) to (Tf-V) can be removed. It is assumed that they are in the form of the formulas (I A) to (JT-K) and (JT-Q) to (Ü-V):

wherein M and the radicals of the respective ligands independently of one another have the abovementioned meaning, each of the formulas (JJ-A) to (H-J) and (H-Q) to (H-V) being particularly preferred per se. In the context of this application, it is assumed that the respective formulas (H-A) to (H-J) and (H-Q) to (H-V) characterize sub-formulas of (la).

The particularly preferred metal complexes of the formula (Ib) with ligands of the formulas (IK) to (IP) and (IW) to (I-ZA) each have 1 ligand of the formulas (ULK) to (IH- P) and (TH-W) to (HI-ZA) can be removed. It is assumed that they are in the form of the formulas (IH-K) to (IH-P) and (TH-W) to (HI-ZA):

wherein M, An ^" and the residues of the respective ligands independently of one another have the abovementioned meaning, with each of the formulas (HI-K) to (IH-P) and (JH-W) to (HI-ZA) being particularly preferred per se In the context of this application it is assumed that the respective formulas (HT-K) to (IH-P) and (Tfl-W) to (HI-ZA) characterize sub-formulas of (Ib).

All monovalent anions or an equivalent of a polyvalent anion or an equivalent of an oligomeric or polymeric anion are suitable as anions An ^" . They are preferably colorless anions. Suitable anions are, for example, chloride, bromide, iodide, nitrate, tetrafluoroborate, perchlorate, Hexafluorosilicate, hexafluorophosphate, methosulfate, ethosulfate, C cio-alkanesulfonate, C _r Cιo-perfluoroalkanesulfonate, optionally substituted by chlorine, hydroxy, Cι-C - alkoxy Cio-alkanoate, optionally by nitro, cyano, hydroxy, Cι-C ₂₅ - Alkyl, perfluoro-C ₄ alkyl, C 1 -C alkoxycarbonyl or chlorine substituted benzene or naphthalene or biphenyl sulfonate, optionally by nitro, cyano, hydroxy, C 1 -C ₄ alkyl, C 1 -C alkoxy, C 1 -C ₄ -Alkoxycarbonyl or chlorine-substituted benzene or naphthalene or biphenyl disulfonate, optionally by nitro, cyano, C 1 -C ₄ alkyl, C 1 -C ₄ alkoxy, C 1 -C alkoxycarbonyl, benzoyl, chlorobenzoyl or toluoyl sub substituted benzoate, the anion of naphthalenedicarboxylic acid, diphenyl ether disulfonate, tetraphenyl borate, cyanotriphenyl borate, tetra-C ₁ -C ₂ o-alkoxyborate, tetraphenoxy borate, 7,8- or 7,9-dicarba-nido-undecaborate (l-) or (2-) ), which are optionally substituted on the B and / or C atoms by one or two Ci-Cπ-alkyl or phenyl groups, dodecahydro-dicarbadodecaborate (2-) or B-Cι-Ci2-alkyl-C-phenyl -dodecahydro-dicarbadodecaborate (l-), polystyrene sulfonate, poly (meth) acrylate, polyallylsulfonate.

Bromide, iodide, acetate, tetrafluoroborate, perchlorate, hexafluorophosphate, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, toluenesulfonate, dodecylbenzenesulfonate, tetra-decanesulfonate, polystyrene sulfonate are preferred.

Furthermore, all monovalent anions or an equivalent of a polyvalent anion of a dye can be used as anions An ^" . The anionic dye An ^" preferably has an absorption spectrum similar to that of the cationic metal complex salt. Suitable examples are anionic azo dyes, anthraquinone dyes, porphyrins, phthalocyanines, subphthalocyanines, cyanines, merocyanines, rhodamines, metal complexes, oxonols and derivatives of flavonic acid.

Metal complexes of the formula (Ia), in particular of the formein (HA) to (HC), (HG), (π-H), (HJ), (HK), (HQ), (HR) and (HU )

wherein M stands for Pd, Fe, Zn, Cu, Ni or Co and

the other radicals have the meanings which are particularly preferred and very particularly preferred above under the formulas (IA) to (IC), (IG), (IH), (IJ), (IK), (IQ), (IR) and (IU) own, with each formula being particularly preferred in itself.

Metal complexes of the formula (Ib), in particular of the formulas (ffl-), (LTJ-L), (HI-O), (IH-W) and (H-X), are also very particularly preferred,

wherein

M represents Pd, Fe, Zn, Cu, Ni or Co,

An ^"stands for bromide, iodide, acetate, tetrafluoroborate, perchlorate, hexafluorophosphate, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, toluenesulfonate, dodecylbenzenesulfonate, tetradecanesulfonate, polystyrene sulfonate and

the other radicals have the meanings which are particularly preferred and very particularly preferred above under the formulas (I-K), (I-L), (I-W) and (I-X),

each formula being particularly preferred in itself.

Preferred examples of metal complexes of the formulas (H-A) to (H-K) and (H-Q) to (H-V) are:

(HA):

(HB)

(H-C):

(Π-D):

(HG):

(H-J):

(3)

(4)

(6) (HK).

(II-Q):

Preferred examples of metal complexes of the formulas (HI-K) to (IH-P) and (IH-W) to (HI-ZA) are:

(HI-K):

(HI-L):

or in deprotonated form:

or in deprotonated form:

(IH-O):

The light-absorbing 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., but at least greater than 200 ° C. Such a change can be, for example, a decomposition or chemical change in the chromophoric center of the light-absorbing compound.

For the optical data carrier according to the invention, which is written and read with the light of the wavelength 360 to 460 nm, in particular that of a blue laser, those metal complexes are preferred as light-absorbing compounds whose absorption maximum λm _M ι is in the range from 340 to 410 nm , where the wavelength λι ₂ , at which the extinction in the short-wave flank of the absorption maximum of wavelength λ _max i is half the extinction _value at λ _maxl , and the wavelength λι _/ ιo, at which the absorbance in the short-wave flank of the absorption maximum of the wavelength λ _max i is one tenth of the absorbance value at λ _max i, preferably not more than 50 nm apart. Such a metal complex preferably does not have a longer-wave maximum X ^ _n a up to a wavelength of 500 nm, particularly preferably up to 550 nm, very particularly preferably up to 600 nm.

Metal complexes with an absorption maximum λ _max i of 345 to 40O nm, in particular 350 to 390 nm, very particularly preferably 360 to 380 nm, are preferred.

The metal complexes λm and λyio, as defined above, are preferably not more than 40 nm apart, more preferably not more than 30 nm apart, very particularly preferably not more than 20 nm apart.

For the optical data carrier according to the invention, which is written and read with the light of the wavelength 360 to 460 nm, in particular that of a blue laser, metal complexes are preferred as light-absorbing compounds whose absorption maximum λ _{maώ is} in the range 420 to 550 nm, the Wavelength λι _{/ 2} , at which the extinction in the short-wave flank of the absorption maximum of wavelength _m ^ is half the extinction _value at λ _max2 , and the wavelength λyι ₀ , at which the extinction in the short-wave flank of the absorption maximum of wavelength λ _{max2 is} one tenth of the extinction value at λ _ma ^, preferably not more than 80 nm apart. Such a metal complex preferably does not have a shorter-wave maximum λmaxx up to a wavelength of 350 nm, particularly preferably up to 320 nm, very particularly preferably up to 290 nm.

Metal complexes with an absorption maximum λ _m ^ of 430 to 550 nm, in particular 440 to 530 nm, very particularly preferably 450 to 520 nm are preferred. The metal complexes λι _{/ 2} and λ _W , as defined above, are preferably not more than 70 nm apart, more preferably not more than 50 nm apart, very particularly preferably not more than 40 nm apart.

At the absorption maximum λ _max ι or _m ^, the metal complexes 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 metal complexes with the preferred spectral properties are, in particular, those which have a low solvatochromism (dioxane / DMF or methylene chloride / methanol). Metal complexes are preferred whose solvatochromism Δλ _DD = | λ _DMF - λ _D ; _oxane |, ie the positive difference of the absorption _wavelengths in the solvents dimethylformamide and dioxane, or their solvatochromism Δ _MM = | λMethanoi -

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.

The optical data carrier according to the invention, which is written and read with the light of a blue laser, is preferred. The laser wavelength is preferably in the range from 360 to 460 nm, particularly preferably in the range from 390 to 420 nm, very particularly preferably in the range from 400 to 410 nm. The laser optics preferably have a numerical aperture NA> 0.6, particularly preferably> 0 , 7, very particularly preferably> 0.8.

The optical data carrier is preferably written and read at the same wavelength.

The metal complexes used according to the invention guarantee a sufficiently high reflectivity (preferably> 10%, in particular> 20%) of the optical data carrier in the blank state as well as 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 of 360 up to 460 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 that have changed after thermal degradation. The k value (imaginary part of the complex refractive index) of the formation layer, consisting of the metal complexes used according to the invention, is preferably in the range from 0.01 to 0.40, preferably in the range from 0.01 to 0.30, particularly preferably in the range from 0.01 to 0.20.

The n-value (real part of the complex refractive index) of the information layer, consisting of the metal complexes used according to the invention, is preferably in the range from 0.9 to L3 or 1.7 to 2.8, preferably in the range from 0.9 to 1.2 or 1.8 to 2.8, particularly preferably in the range from 0.9 to 1.1 or 1.9 to 2.8.

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. Spin coating is carried out from solution or dispersion. The metal complexes according to the invention 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. The solutions of the metal complexes listed above are preferably used for spin coating.

The information layer preferably consists of at least 70%, preferably at least 85%, particularly preferably at least 95%, very particularly preferably 100% of a metal complex according to the invention.

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, protective layers and cover layers. Metals and dielectric layers serve among other things to adjust the reflectivity and the heat balance. Depending on the laser wavelength, metals can be gold, silver, aluminum, etc. his. Dielectric layers are, for example, silicon dioxide and silicon nitride. Protective layers or cover layers are, for example photocurable lacquers, (pressure-sensitive) adhesive layers and protective films.

Silicon dioxide and silicon nitride are applied, for example, by so-called reactive sputtering. The layer thicknesses are, for example, in the range from 1 nm to 40 nm.

The metal layers are applied, for example, by sputtering. The layer thicknesses are, for example, in the range from 10 to 180 nm.

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. Protective films are preferably made of translucent material, preferably plastic films. Suitable materials are, for example, polycarbonate, copolycarbonates, PMMA and cyclic polyolefins. The thickness is, for example, 5 to 200 μm, preferably 10 to 180 μm, particularly preferably 20 to 150 μm, very particularly preferably 50 to 120 μm.

Photocurable lacquers are, for example, UV-curable lacquers. These are, for example, acrylates and methacrylates, such as those from P.K.T. Oldring (Ed.), Chemistry & Technology of UV & EB Formulations for Coatings, Inks & Paints, Vol. 2, 1991, SITA Technology, London, pp. 31-235 are known. The thickness is, for example, 5 to 200 μm, preferably 10 to 180 μm, particularly preferably 20 to 150 μm, very particularly preferably 50 to 120 μm.

In addition, the optical data carrier preferably contains at least one substrate. The substrate material is preferably transparent. Its thickness is at least 0.3 mm, preferably at least 0.6 mm and very particularly preferably at least 1.1 mm. Suitable substrate materials are preferably transparent thermoplastics or thermosets. Suitable thermoplastics are, for example, polycarbonate, copolycarbonates, PMMA and cyclic polyolefins.

The optical data carrier according to the invention has, for example, the following layer structure (cf. FIG. 1): a preferably transparent substrate (1), optionally a reflection layer (7), optionally a protective layer or dielectric layer (2), an information layer (3), optionally one Protective layer or dielectric layer (4), optionally an adhesive layer (5), a cover layer (6). The arrows shown in Fig. 1 and Fig. 2 represent the path of the incident light.

The structure of the optical data carrier can preferably include: 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 or dielectric 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 reflection layer (7), 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 or dielectric layer (4), optionally one 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 or dielectric layer (2), at least one information layer (3) which can be rubbed with light, preferably laser light, optionally an adhesive layer (5), and a transparent cover layer (6) are applied are.

- Contain a preferably transparent substrate (1), on the surface of which a protective layer or dielectric layer (2), a reflection layer (7), at least one information layer (3) which can be written on with light, preferably laser light, optionally a protective layer or dielectric 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 there is optionally a protective layer or dielectric layer (2), at least one information layer (3) that can be written on with light, preferably laser light, optionally a protective layer or dielectric 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 can have, for example, the following layer structure (cf. FIG. 2): a preferably transparent substrate (11), an information layer (12) that can be written on with light, preferably laser light, optionally a reflection layer (13), optionally one Adhesive layer (14), another preferably transparent substrate (15).

The optical data carrier preferably contains an information layer (3) or (12).

The optical data carrier likewise preferably contains a reflection layer (7) or (13).

The optical data carrier likewise preferably contains a transparent cover layer (6).

The optical data carrier likewise preferably contains a substrate (1) or (11) or (15) made of polycarbonate or copolycarbonate.

The substrate (1) likewise preferably has a thickness of 0.3 to 1.5 mm, preferably 0.5 to 1.2 mm, in particular 1.1 mm.

The substrate (11) and (15) likewise preferably has a thickness of 0.3 to 1.5 mm, preferably 0.5 to 1.2 mm, in particular 0.6 mm. The structure of the optical data carrier is particularly preferred as follows:

a transparent substrate (1), on the surface of which a reflection layer (7), an information layer (3) which can be written and read with light, preferably laser light, a protective layer or dielectric layer (4), an adhesive layer (5), and a transparent cover layer (6) are also applied. The structure of the optical data carrier is also particularly preferred as follows:

a transparent substrate (1), on the surface of which a reflection layer (7), an information layer (3) that can be written and read with light, preferably laser light, a protective layer or dielectric layer (4), and a transparent cover layer (6) are applied.

The structure of the optical data carrier is also particularly preferred as follows:

a transparent substrate (1), on the surface of which a reflection layer (7), an information layer (3) which can be written and read with light, preferably laser light, and a transparent cover layer (6) are applied.

a transparent substrate (1), on the surface of which a reflection layer (7), a protective layer or dielectric layer (2), an information layer (3) which can be written and read with light, preferably laser light, a protective layer or dielectric layer (4), a Adhesive layer (5), and a transparent cover layer (6) are applied.

a transparent substrate (1), on the surface of which a reflection layer (7), a protective layer or dielectric layer (2), an information layer (3) which can be written and read with light, preferably laser light, a protective layer or dielectric layer (4), and a transparent cover layer (6) is applied.

a transparent substrate (1), on the surface of which a reflection layer (7), a protective layer or dielectric layer (2), an information layer (3) which can be written and read with light, preferably laser light, and a transparent cover layer (6) are applied.

The structure of the optical data carrier is also particularly preferred as follows: a transparent substrate (1), on the surface of which a protective layer or dielectric layer (2), an information layer (3) which can be written and read with light, preferably laser light, a protective layer or dielectric layer (4), an adhesive layer (5), and a transparent cover layer (6) is applied.

a transparent substrate (1), on the surface of which a protective layer or dielectric layer (2), an information layer (3) which can be written and read with light, preferably laser light, a protective layer or dielectric layer (4), and a transparent cover layer (6) are upset.

a transparent substrate (1), on the surface of which a protective layer or dielectric layer (2), an information layer (3) which can be written and read with light, preferably laser light, and a transparent cover layer (6) are applied.

a transparent substrate (11), an information layer (12) which can be written and read with light, preferably laser light, a reflection layer (13), an adhesive layer (14), a further transparent substrate (15).

The invention also relates to optical data carriers which contain two information layers. For example, they can be constructed as follows: - a cover layer (6), optionally an adhesive layer (5), optionally a protective layer or dielectric layer (4), an information layer (3), optionally a protective layer or dielectric layer (2), optionally a reflection - Layer (7), a transparent substrate (1), optionally a reflection layer (7), optionally a protective layer or dielectric layer (2), an information layer (3), optionally a protective layer or dielectric layer (4), optionally one Adhesive layer (5), a cover layer (6). a preferably transparent substrate (11), an information layer (12), optionally a reflection layer (13), optionally an adhesive layer (14), optionally a protective or dielectric layer, optionally an adhesive layer (14), optionally a reflection layer (13), an information layer (12), another preferably transparent substrate (15). a cover layer (6), optionally an adhesive layer (5), optionally a protective layer or dielectric layer (4), an information layer (3), optionally a protective layer or dielectric layer (2), optionally a reflective layer (7), a protective layer or dielectric layer (4), an information layer (3), optionally a protective layer or dielectric layer (2), optionally a reflection layer (7), optionally a protective layer or dielectric layer (4), a transparent substrate (1). - A preferably transparent substrate (11), an information layer (12), optionally a reflection layer (13), optionally an adhesive layer (14), optionally a protective or dielectric layer, an information layer (12) optionally a reflection layer (13) further, preferably transparent substrate (15). - a preferably transparent substrate (11), an information layer (12), optionally a reflection layer (13), optionally a protective or dielectric layer, an information layer (12), optionally a reflection layer (13), optionally an adhesive layer (14), a further, preferably transparent substrate (15).

These optical data carriers with two information layers can also contain all of the preferred layer structures listed above in an analogous manner.

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

The invention further relates to a method for producing the optical data carrier according to the invention, which is characterized in that a preferably transparent substrate, optionally already coated with a reflection layer, with at least one metal complex as the light-absorbing compound and having at least one ligand of the formula (I), optionally coated in combination with suitable binders and additives and optionally solvents and optionally provided with a reflection layer, further intermediate layers and optionally a protective layer or a further substrate or a covering layer. The invention further relates to metal complexes which have at least one ligand of the formula (I), in which the rest of the formula

for ~ N = N-, -CR ^{1 =} N-, -CR ^ CR ² -, -N = CR ² -, -N = NN = CR ⁴ -, -CR ¹ = CR ² -N = CR ⁴ - or -CR ^ CR ^ CR ^ CR ⁴ -, stands,

wherein R ¹ to R ⁴ and the remaining radicals, unless they have been defined, have the meaning given above.

The preferred ranges for the metal complexes according to the invention also correspond to those given above.

Metal complexes which contain at least one ligand of the formula (I-A), (IB), (ID) to (IL), (IN) to (IR), (T) to (IX), (LZ) and. Are particularly preferred (I-ZA), where in formula (IA), (IB) and (IK) at least one of the rings A, A 'and B has at least one substituent from the series of the branched C ₃ -C ₈ alkoxy radicals, for example -0 -CH ₂ -CH (CH ₃ ) ₂ , -0-CH [CH (CH ₃ ) ₂ ] ₂ , -0-C (CH ₃ ) ₃ , -0-CH2-CH (C ₂ H ₅ ) (C ₄ H ₉ ), -0-CH ₂ -C (CH ₃ ) ₂ -C ₂ H ₅ , of the branched or ring-closed C ₂ -C ₈ alkylamomethylene residues, for example CH ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -CH ₂ NH-CH2-CH (C ₂ H ₅ χC ₄ H9), -CH ₂ NH-CH [CH (CH ₃ ) 23 ₂ ,

the optionally branched C ₂ -C ₅ alkoxycarbonyl radicals, for example -COOCH ₂ CH ₃ , -COO-CH (CH ₃ ) ₂ , -COO-CH [CH (CH ₃ ) ₂ ] 2, the optionally branched or ring-closed C ₂ - C ₈ alkylaminosulfonyl radicals, for example -S0 ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -S0 ₂ NHCH ₂ CH (CH ₃ ) ₂ , -S0 ₂ NHC (CH ₃ ) ₂ CH ₂ CH ₃ , -S0 ₂ NHC (CH ₃ ) ₃ , -S0 ₂ NH- (CH ₂ CH ₂ CH ₂ 0-) ₂ CH ₃ ,

-S0 ₂ NH- (CH ₂ CH ₂ CH ₂ 0) - (CH ₂ CH ₂ θ) -CH3, -S0 ₂ N (CH ₂ CH0H) ₂ ,

S0 ₂ N (CH ₂ CH (CH ₃ ) CH ₂ OH) _2j

wearing. Metal complexes of the formulas (HA), (HB), (HD) to (HK), (HQ), (H-R), (HT) to (HV), (HLK), (DLT-L), (HI-N) to (IH-P), (IH-W), (HI-X), (HI-Z) and (HI-ZA), where in formula (HA), (HB) and (IH- K) at least one of the rings A, A 'and B at least one substituent from the series of the branched C ₃ -C ₈ alkoxy radicals, for example -0-CH ₂ -CH (CH ₃ ) ₂ , -0-CH [CH (CH ₃ ) ₂ ] ₂ , -0-C (CH ₃ ) ₃ , -O-CTα-CH ^ Hs) ^^), -0-CH ₂ -C (CH ₃ ) 2-C ₂ H ₅ , the branched or ring-closed C ₂ -C ₈ alkylaminomethylene residues, for example -CH ₂ N (CH ₂ CH (CH3) 2) 2, -CH ₂ NH-CH ₂ -CH (C ₂ H ₅ ) (C ₄ H ₉ ), -CH ₂ NH-CH [CH (CH ₃ ) ₂ ] 2,

the optionally branched C ₂ -C ₅ alkoxycarbonyl radicals, for example -COOCH2CH3, -COO-CH (CH ₃ ) ₂ , -COO-CH [CH (CH ₃ ) ₂ ] ₂ , the optionally branched or ring-closed C ₂ -C ₈ -Alkylaminosulfonylreste, for example -S0 ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -S0 ₂ NHCH ₂ CH (CH ₃ ) ₂ , -S0 ₂ NHC (CH ₃ ) ₂ CH ₂ CH ₃ , -S0 ₂ NHC (CH ₃ ) ₃ , -S0 ₂ NH- (CH ₂ CH ₂ CH ₂ 0-) ₂ CH ₃ ,

-S0 ₂ NH- (CH ₂ CH ₂ CH ₂ 0) - (CH ₂ CH ₂ θ) -CH ₃ , -S0 ₂ N (CH ₂ CHOH) ₂ ,

S0 ₂ N (CH2CH (CH3) CH ₂ OH) _2j

wearing.

Metal complexes of the formulas (HD) to (HK), (HQ), (Tf-R), (HT) to (HV), (HI-L), (HI-N) to (IH-P) are very particularly preferred. , (IH-W), (HI-X), (HI-Z) and (HI-ZA) as specified above as examples.

The metal complexes according to the invention are marketed in particular as powders or granules or as a solution, the latter preferably with a solids content of at least 2% by weight. The granulate form is preferred, in particular granules with an average particle size of 50 μm to 10 mm, in particular 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 having 3 to 6 carbon atoms, preferably propanol, butanol, pentanol, hexanol, diacetone alcohol or also mixtures of these alcohols, such as, for example, 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.

Solutions containing are also preferred

a) at least one metal complex according to the invention and b) at least one organic solvent.

Solutions containing are particularly preferred

a) a metal complex according to the invention and b) an organic solvent.

They are preferably at least 1% by weight, preferably at least 2% by weight, particularly preferably at least 5% by weight, in the metal complexes according to the invention, in particular those of the formulas (Ia) to (Ic), (HA) to (HK), (HQ) to (HU), (HI-K) to (IH-P) and (IH-W) to (HI-ZA). 2,2,3,3-Tetrafluoropropanol, 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 solution particularly preferably consists of more than 95% by weight, in particular more than 98% by weight, of components a) and b).

The invention further relates to a process for the preparation of the metal complexes according to the invention, which is characterized in that a metal salt with a ligand compound of the formula (Id)

worm

A represents an optionally substituted and / or benzyl or naphthane-fused five- or six-membered aromatic or quasi-aromatic or partially hydrogenated heterocyclic radical,

n represents 0 or 1, Y ^{1 represents} N or CR ¹ ,

Y ^{2 represents} N or CR ² ,

Y ^{3 represents} N or CR ³ ,

X represents O, S or NR ⁵ ,

R ^{5 represents} hydrogen, alkyl, alkenyl, aralkyl, cycloalkyl, acyl, aryl or a heterocyclic radical,

R ¹ to R ⁴ independently of one another represent hydrogen, halogen, alkyl, alkoxy, mono- or dialkylamino, aralkyl, aryl, hetaryl, arylazo, hetarylazo, cyano or alkoxycarbonyl,

R *; R ^{2 can form} an optionally substituted and / or optionally containing heteroatoms triatomic bridge or an optionally substituted fouratoms bridge which contains no or at least 2 heteroatoms,

R; R ³ and R ⁴ ; R ⁵ can each independently form a bridge and

R ² ; R ⁵ can form a bridge if n stands for 0,

and wherein the rest of the formula

for -N = N-, -CR ^ N-, -CR ^ CR ¹ -, -N = CR ² -, -N = NN = CR ⁴ -, -CR ¹ = CR ² -N = CR ⁴ - or - CR ¹ = CR ² -CR ³ = CR ⁴ -, stands,

implements.

Two or more different ligand compounds of the formula (Id) can also be used in this process according to the invention. A statistical mixture of metal complexes which contain two identical ligands of the formula (I) and those complexes which contain two different ligands of the formula (I) is then obtained. These mixtures are also the subject of the invention. 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 usually 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, 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 sulfonic acids such as methanesulfonates, trifluoromethanesulfonates or to understand benzenesulfonates of the corresponding metals. Metal salts are also to be understood as meaning complexes with ligands other than those of the formulas (Ia), in particular complexes of acetylacetone and acetoacetic acid esters. Examples of suitable metal salts are: 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. The acetates of the metals are preferred. The metals of the underlying metal salts are preferably divalent.

Alkali acetates such as e.g. Sodium acetate, potassium acetate, alkali hydrogen carbonates, carbonates or hydroxides such as e.g. Sodium hydrogen carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, or amines such as e.g. Ammonia, dimethylamine, triethylamine, diethanolamine. Such basic substances are particularly advantageous when metal salts of strong acids such as e.g. the metal chlorides or sulfates are used.

Suitable solvents are water, alcohols such as e.g. Methanol, ethanol, propanol, butanol, 2,2,3,3-tetrafluoropropanol, ethers such as dibutyl ether, dioxane or tetrahydrofuran, aprotic solvents such as e.g. Dimethylformamide, N-methylpyrrolidone, acetonitrile, nitromethane, dimethyl sulfoxide. Methanol, ethanol and 2,2,3,3-tetrafluoropropanol are preferred.

The vinylogenic amidines and amides, hereinafter called ligand compounds, of the formula (Id) required for the preparation of the metal complexes according to the invention are also the subject of this invention. The invention further relates to the use of the metal complexes according to the invention as light-absorbing compounds in the information layer of write-once optical data carriers which can be written and read with blue light with a wavelength in the range from 360-460 nm, in particular laser light.

The invention also relates to ligand compounds of the formula (Id)

wherein

n represents 0 or 1,

Y ^{1 represents} N or CR ¹ ,

Y ^{2 represents} N or CR ² ,

Y ^{3 represents} N or CR ³ ,

X represents O, S or NR ⁵ ,

R ^X ; R ^{2 can form} an optionally substituted and / or optionally containing triatomic bridge or an optionally substituted four-atom bridge which contains no or at least 2 heteroatoms,

R ² ; R ³ and R ⁴ ; R ⁵ can each independently form a bridge and

R ² ; R ⁵ can form a bridge when n is 0 and in which the rest of the formula

for -N = N-, -CR ^ N-, -CR ^ CR ¹ -, -N = CR ² -, -N = NN = CR ⁴ -, -CR ^J = CR -N = CR ⁴ - or -CR ¹ = CR ² -CR ³ = CR ⁴ -.

Preferred ligand compounds correspond to the protonated form of at least one of the formulas (IA), (IB), (ID) to (IL), (IN) to (IR), (LT) to (IX), (LZ) and (I-ZA ) or a tautomeric form thereof, wherein in formula (IA) and (IB) at least one of the rings A and B at least one substituent from the series of branched C ₃ -C ₈ alkoxy radicals, for example -0-CH ₂ -CH (CH ₃ ) ₂ , -0-CH [CH (CH ₃ ) ₂ ] ₂ , -0-C (CH ₃ ) ₃ , -0-CH ₂ -CH (C ₂ H ₅ ) (C ₄ H ₉ ),

-0-CH ₂ -C (CH ₃ ) ₂ -C ₂ H ₅ , the branched or ring-closed C ₂ -C ₈ alkylaminomethylene radicals, for example -CH ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -CH ₂ NH-CH ₂ -CH (C ₂ H ₅ ) (C ₄ H ₉ ),

-CH ₂ NH-CH [CH (CH ₃ ) ₂ ] ₂ ,

the optionally branched C ₂ -C 5 alkoxycarbonyl radicals, for example -COOCH2CH3, -COO-CH (CH ₃ ) ₂ , -COO-CH [CH (CH ₃ ) ₂ ] _25, the optionally branched or ring-closed C ₂ -C ₈ alkylaminosulfonyl radicals, for example, -S0 ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -S0 ₂ NHCH ₂ CH (CH ₃ ) ₂ , -S0 ₂ NHC (CH ₃ ) ₂ CH ₂ CH ₃ , -S0 ₂ NHC (CH ₃ ) ₃ , -S0 ₂ NH- (CH ₂ CH ₂ CH ₂ 0-) ₂ CH ₃ ,

-S0 ₂ NH- (CH ₂ CH ₂ CH ₂ 0) - (CH ₂ CH ₂ 0) -CH3, -S0 ₂ N (CH ₂ CHOH) ₂ ,

S0 ₂ N (CH ₂ CH (CH ₃ ) CH ₂ OH) _2j

wearing.

Ligand compounds of the formula (Id) can be prepared analogously to J. Org. Chem. 2002, 67, 5753, Khim. Geterotsycl. Soedin. 2 (1966) 506, Pharm. Chem. J. (Engl. Transl.) 7 (1973) 199, Z. Electrochem. 64 1960) 720, Gazz. Chim. Ital. 124 (1994) 301 or according to CR Hebd. Seance Acad. Be. 240 (1955) 983, J. Chem. Soc. Perkin Trans. H, 19842111. In this invention, all combinations of the above disclosed general ranges and the preferred ranges and the preferred range apply to each other as revealed ago ^¬ preferred ranges.

The following examples illustrate the subject matter of the invention.

Examples

example 1

a) 5 g of bis-benzothiazol-2-yl-amine were introduced into 20 ml of chlorosulfonic acid and stirred overnight. 5 g of thionyl chloride were added and the mixture was stirred at 50 ° C. for 1 h. After cooling to room temperature, the mixture was poured onto 200 g of ice, filtered off with suction and immediately mixed with the remaining ice with 8.7 ml of diisobutylamine. After warming to room temperature, the mixture was made alkaline with about 0.5 ml of 50% strength by weight sodium hydroxide solution. It was filtered off, washed with water and dried at 50 ° C in a vacuum. 11.1 g (95% of theory) of a yellow powder of the formula were obtained

MS: m / e = 665

UV (CH ₂ C1 ₂ ): λ ^ = 359, 376 nm.

b) 2.48 g of the product from a) were stirred in 20 ml with 1.25 g of nickel acetate tetrahydrate overnight at room temperature. It was then filtered off, washed with methanol and water and dried at 50 ° C in a vacuum. 1.8 g (70% of theory) of a beige powder of the formula were obtained

Mp = 173-175 ° C

MS: m / e = 1388

UV (CH ₂ C1 ₂ ): = 365, 376 nm.

A 2% by weight solution in TFP (2,2,3,3-tetrafluoropropanol) applied to a glass plate gives a glass-like transparent film.

Example la

The corresponding cobalt complex could be prepared in an analogous manner.

Mp = 238-240 ° C

MS: me = 1387

UV (CH ₂ C1 ₂ ): λ ^ = 363, 378 nm.

Example lb

5 g of bis (4-methyl-5-ethoxycarbonyl-thiazol-2-yl) methane were stirred in 20 ml of ethanol with 1.8 g of cobalt acetate tetrahydrate at 60 ° C. for 4 h. After cooling, the product was filtered off with suction, washed with ethanol and water and dried at 50 ° C. in vacuo. 5.0 g (93% of theory) of a yellow powder of the formula were obtained

MS: m / e = 765

UV (CH ₂ C1 ₂ ): λ ^ = 455 nm.

Analogous to the previous examples, the examples in the following table were also produced. Table 1

Example 2

1.1 g of the hydrazone of the formula

were stirred in 10 ml of methanol together with 0.47 g of nickel acetate tetrahydrate overnight at room temperature. The orange suspension was filtered off, washed with methanol and water and dried at 50 ° C in a vacuum. 1.12 g (99% of theory) of an orange powder of the formula were obtained

Mp = 248-253 ° C MS: m / e = 592 UV (CH ₂ C1 ₂ ): = 472 nm.

Analogously to example 2, the examples in the table below were also prepared.

Table 2

Example 3a) 2.49 gl, l-bis- (methylthio) -2-cyano-3-phenyl-l-propen-3-one and 1.25 g of o-aminothiophenol were stirred in 60 ml of ethanol for 6 hours under a nitrogen atmosphere , After cooling, the product was filtered off with suction, washed with a little ethanol and dried at 50 ° C. in vacuo. 2.4 g (86% of theory) of a colorless powder of the formula were obtained

Mp = 238-240 ° C.

b) 0.7 g of the product from a) were stirred in 6 ml of methanol with 0.62 g of nickel acetate tetrahydrate overnight at room temperature. It was filtered off, washed with methanol and dried at 50 ° C in a vacuum. 0.65 g (85% of theory) of a greenish yellow powder of the formula was obtained

Mp> 280 ° C

UV (CH ₂ C1 ₂ ): λ ,,,, «= 362 nm.

Example 3b

a) 2.6 g of the barbituric acid derivative of the formula

and 1.25 g of o-aminothiophenol were boiled in 40 ml of ethanol for 4.5 hours under a nitrogen atmosphere. The suspension was filtered off, washed with ethanol and dried in vacuo at 50 ° C. 2.6 g (90% of theory) of a yellowish powder of the formula were obtained

Mp> 280 ° C

λ _max = 348 nm in dichloromethane.

b) 0.72 g of the product from a) and 0.62 g of nickel acetate tetrahydrate were stirred in 6 ml of methanol overnight at room temperature. It was filtered off with suction, washed with methanol and dried at 50 ° C. in vacuo, giving 0.62 g (78% of theory) of a pale green powder of the formula

Mp> 280 ° C

^: 390 nm in dichloromethane.

The examples in the table below were also prepared analogously to Example 3.

Table 3

Example 4 a) 22.9 g of l-amino-3-imino-isoindole, 63.3 g of 2-amino-5-diisopropylaminol, 3,4-thiadiazole and 3 g of ammonium chloride were stirred under reflux in 200 ml of ethanol for 24 hours. After cooling, it was introduced into 300 ml of petroleum ether, suction filtered, washed with petroleum ether and water and dried at 50 ° C. in vacuo. 58.8 g (73% of theory) of an orange powder of the formula were obtained

Mp = 192-195 ° C.

b) 0.13 g of cobalt acetate tetrahydrate were placed in 20 ml of acetonitrile. 3 drops of 65% by weight Nitric acid was added. A solution was formed after 30 minutes. 0.27 g of the product from a) were added. After 1 h at 50 ° C., the mixture was cooled, diluted with 20 ml of water and precipitated with lithium perchlorate. After suction, ^" washing with water and drying at 50 ° C. in vacuo, 0.46 g (78% of theory) of a red powder of the formula

MS: m / e = 1079 (ML ₂ ⁺ )

UV (CH ₂ C1 ₂ ): _∞ = 453, 501 nm.

A 2 wt. Solution in TFP (2,2,3,3-tetrafluoropropanol) applied to a glass plate gives a glass-like transparent film.

Example 4a

1.3 g of nickel acetate tetrahydrate were dissolved in 30 ml of ethanol. 2.6 g of the product from Example 4, paragraph a) were added. The mixture was stirred at room temperature for 2 h and then lithium perchlorate was added. After stirring for 2 h, the mixture was precipitated by adding water. It was filtered off, washed with water and dried in vacuo at 50 ° C. 2.06 g of an orange powder were obtained, which was stirred with toluene at room temperature. The insoluble residue was washed with suction and dried in vacuo at 50 ° C. 1.09 g of an orange powder of the formula were obtained

MS: m / e = 568 (ML ⁺ ) UV (CH ₂ Cl ₂ ): λ _πιax = 449 nm.

From the toluene mother liquor, 1.5 g of another orange powder of the formula could be spun in

be isolated.

MS: m / e = 1079 (M + Ε?) UV (CH ₂ C1 ₂ ): _∞ = 405, 430, 476, 506, 549 nm.

Example 5

a) 2.18 g of 1,3-diiminoisoindolenine were dissolved in 50 ml of methanol and a solution of ethyl cyanoactetate in 20 ml of methanol was added dropwise at 20 ° C. The mixture was stirred at 60 ° C. for 8 hours and then at room temperature overnight. The precipitated solid was filtered off, washed with a little methanol and dried at 50 ° C in a vacuum. 4.52 g (89% of theory) of a yellow powder of the formula were obtained

Mp = 247 - 249 ° C

UV (acetone): λ _max = 393, 416 nm.

b) 0.31 g of the product from a) were stirred in 10 ml of DMF with 0.50 g of nickel acetate tetrahydrate for 4 hours at 100 ° C. 10 ml of water were added to the solution and the precipitated solid was filtered off, washed with water and dried at 50 ° C. in vacuo. 0.18 g (42% of theory) of a yellow powder of the formula were obtained

Mp> 350 ° C UV (acetone): ^ = 453, 482 nm.

The following examples were also prepared analogously. Example 5a

UV (acetone): X ^ = 477, 510 nm

Mp> 350 ° C

UV (acetone): λ _max ⁼ 522, 563 nm

Example 5b

UV (CH ₂ C1 ₂ ): λ- _na x = 407, 430 nm

Mp> 350 ° C UV (CH ₂ C1 ₂ ): λ ^ = 383, 482 nm

Example 5c

UV (acetone): λ _m a _x = 487, 524 nm

Example 6

a) 4.89 g of 2-methylpyridine were dissolved in 5 ml of NMP and 9.13 g of 3-iminophthalimidine hydrochloride were added in portions at 120 ° C. The solution was stirred for a further 16 hours at 130 ° C., stirred in 100 ml of water and the precipitated solid was filtered off with suction, washed with water and dried at 50 ° C. in vacuo. 7.99 g (72% of theory) of a beige powder of the formula were obtained

Mp = 119 - 121 ° C UV (acetone): ^ = 357 nm b) 0.44 g of the product from a) were stirred in 10 ml of DMF with 0.25 g of nickel acetate tetrahydrate for 4 hours at 100 ° C. The precipitated solid was filtered off, washed with ether and dried at 50 ° C. in vacuo. 0.32 g (64% of theory) of a greenish powder of the formula was obtained

Mp> 350 ° C

UV (MeOH): λ ^ - 392 nm

The following examples were also prepared analogously.

Example 6a

Mp> 350 ° C

UV (MeOH): λ-, _« = 381 nm Example 6b

Mp = 110-112 ° CW (CH ₂ C1 ₂ ): λ ^ = 336 nm

Example 7

A 3% by weight solution of the dye from Example 1 in 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 by injection molding as a disc with a diameter of 12 cm and a thickness of 0.6 mm, and the track pitch of the groove structure was 740 nm. The disc with the dye layer as information carrier was sputtered with 100 nm of silver. A UV-curable acrylic varnish was then applied by spin coating and a second identical polycarbonate substrate was applied. By further spinning, the acrylic varnish is homogeneously distributed over the disk surfaces and then cured using a UV lamp. With a dynamic write test, which was built on an optical bench, consisting of a diode laser (λ = 405 nm), for generating linearly polarized light, a polarization-sensitive beam splitter, a λ / 4 plate and a movably suspended converging lens with a numerical aperture NA = 0.65 (actuator lens), write and read tests were performed. 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 through an astigmatic lens focused on a four-quadrant detector. At a linear velocity V = 3.5 m / s and a write power P, _m γ- = 8.5 mW, a signal-to-noise ratio C / N = 38 dB was measured for HT pits. The write power was applied as an oscillating pulse sequence (see FIG. 3), the disk being alternately irradiated with the above-mentioned write power P _wπ7e and the _{read power} P _rea d «1.9 mW. The write pulse sequence for the HT pit consisted of a leading pulse of length T _top = 1.5T = 60 ns, where T ~ 40 ns is the base time (117 = 440 ns). The leading pulse was placed so that it ended after 3r units. This was followed by eight pulses of length T _mp = 30 ns, the time being determined by T _mp - 0.757 /. The result of this is that a time period ΛT = 10 ns remains free between each write pulse. The 1 I long write pulse was followed by a 1 I long pause. The disc was irradiated with this oscillating pulse sequence until it had turned around once. The marking generated in this way was then _read out with the reading power P _read and the above-mentioned signal-to-noise ratio GW was measured.

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

Claims

claims

1. Optical data carrier, comprising a preferably transparent substrate, possibly already coated with one or more reflection layers and / or protective 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 are applied which can be written and read with blue light, preferably with light having a wavelength in the range from 360-460 nm, in particular 390 to 420 nm, very particularly preferably from 400 to 410 nm, preferably laser light, the information layer being a light-reflecting contains sorbent compound and optionally a binder, characterized in that at least one metal complex is used as the light-absorbing compound, which has at least one ligand of formula (I)

wherein the rest of the formula I (hereinafter referred to as A) is an optionally substituted and / or benz or naphthannelated five- or six-membered aromatic or quasi-aromatic or partially hydrogenated heterocyclic radical, n is 0 or 1, Y ^{1 is} N or CR ¹ stands,

Y ^{2 represents} N or CR ² ,

Y ^{3 represents} N or CR ³ ,

X represents O, S or NR ⁵ ,

R ^{5 represents} hydrogen, alkyl, alkenyl, aralkyl, cycloalkyl, acyl, aryl or a heterocyclic radical, R ¹ to R ⁴ independently of one another represent hydrogen, halogen, alkyl, alkoxy, mono- or dialkylamino, aralkyl, aryl, hetaryl, arylazo, hetarylazo, cyano or alkoxycarbonyl,

R ^X ; R ^{2 can form} an optionally substituted and / or optionally containing heteroatoms triatomic bridge or an optionally substituted fouratoms bridge which contains no or at least 2 heteroatoms,

R ² ; R ³ and R ⁴ ; R ⁵ can each independently form an optionally substituted bridge and

R ² ; R ⁵ can form an optionally substituted bridge if n is 0.

2. Optical data carrier according to claim 1, characterized in that the rest of the formula

for -N = N-, -CR ^J = N-, -CR ^ CR ² -, -N = CR ² -, -CR ¹ = NN = CR ⁴ -, -N = NN = CR ⁴ -, -CR ^ CR ² - N = CR ⁴ - or -CR ¹ = CR ² -CR ³ = CR ⁴ -, particularly preferred for -N = N-, -CRMN ^" -, -CR ^ CR ² -, -N = CR ² - , -N = NN = CR ⁴ -, -CR ^X = CR ² -N = CR ⁴ - or -CR ¹ = CR ² -CR ³ = CR ⁴ -, wherein R ¹ to R ^{4 have} the meaning given in claim 1 have.

3. Optical data carrier according to at least one of claims 1 or 2, characterized in that X stands for NR ⁵ and the rest of the formula -CR ² -N ^Θ -R ⁵ or -CR ⁴ -N ^Θ -R ⁵ for a ring of Formula (X)

wherein the rest of the formula (X) as a protonated tautomer of the formula

is briefly referred to as B and in which B represents an optionally substituted and / or benz or naphthannelated five- or six-membered aromatic or quasi-aromatic or partially hydrogenated heterocyclic radical.

4. Optical data carrier according to at least one of claims 1 to 3, characterized in that it contains, as light-absorbing compounds, at least one metal complex of the formula (Ia), (Ib) or (Ic)>] ₂ + M (Ia),

[O] «2+ (Ib) or NT An

[(' ⁾ JM ³⁺ An (Ic), 2 wherein

M stands for a correspondingly charged metal,

An represents an anion and the rest of the formula (I) has the meanings given in at least one of claims 1 to 3.

5. Optical data carrier according to at least one of claims 1 to 4, characterized in that the metal complex used as the light-absorbing compound has two identical or different ligands of the formulas (I).

6. Optical data carrier according to at least one of claims 1 to 5, characterized in that the metal atom as a metal complex Mg, Ca, Sr, Ba, Cu, Ni, Co, Fe, Zn, Pd, Pt, Ru, Th, Os , Sm, B, AI, Ga, In, V, Cr, Y, La, Ce, Pr, Nd, En, Gd or Tb.

7. Optical data carrier according to at least one of claims 1 to 6, characterized in that A for 2-pyridyl, 2-quinolyl, 2-pyrimidyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,3 -Thiazol-2-yl, l, 3-thiazolin-2-yl, l, 3-thiazol-4-yl, benzothiazol-2-yl, l, 2-thiazol-3-yl, Benzoisothiazol-3-yl, l, 3-oxazol-2-yl, l, 3-oxazolin-2-yl, benzoxazol-2-yl, l, 2-oxazol-3-yl, imidazol-2-yl, hnidazolin 2-yl, benzimidazol-2-yl, idmidazol-4-yl, pyrazol-5-yl, pyrrolin-2-yl, pyrrol-2-yl, l, 3,4-triazol-2-yl, 3H-indoline 2-yl, tetrahydroisoindol-l-yl, isoindol-1-yl, benz (cd) indol-2-yl, l, 3,4-thiadiazol-2-yl, l, 2,4-thiadiazol-5-yl, 1,2,4-thia-diazol-3-yl or l, 3,4-oxadiazol-2-yl, which can optionally be substituted.

8. Optical data carrier according to at least one of claims 1 to 7, characterized in that A for

2-pyridyl is the by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, tert-butoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, tert pentylaminosulfonyl, bis (hydroxyethyl) aminosulfonyl, morpholinosulfonyl, methoxyethoxypropylaminosulfonyl, nitro or cyano may be substituted,

2-Quinolyl is the by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, tert-butoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, tert . -Pentylaminosulfonyl, bis- (hydroxyethyl) aminosulfonyl, morpholinosulfonyl, methoxyethoxypropylaminosulfonyl, nitro or cyano may be substituted, 1,3-thiazol-2-yl which is represented by up to two identical or different chlorine radicals , Fluorine, methoxy, phenyl or cyano can be substituted, benzthiazol-2-yl is, which is up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, tert-butoxy, 2,4 -Dimethyl-3-pentoxy, methoxycarbonyl, di-isobutylaminosulfonyl, tert-pentylaminosulfonyl, bis (hydroxyethyl) aminosulfonyl, morpholinosulfonyl, methoxyethoxypropylaminosulfonyl, nitro or cyano, benzoxazol-2-yl can be substituted by up to two identical or different residues from the chlorine, fluorine, Methyl, methoxy, ethoxy, isobutoxy, tert-butoxy, 2,4-dimethyl-3-pentoxy, methoxycarbonyl, di-isobutylaminosulfonyl, tert-pentylaminosulfonyl, bis (hydroxyethyl) aminosulfonyl, morpholinosulfonyl, Me oxye oxypropylaminosulfonyl, nitro or cyano can be substituted, hnidazol-2-yl, which is composed of up to two identical or different radicals from the series chlorine, methyl, methoxy, phenyl, cyano, -C (= NH) -OCH ₃ , nitro, Methoxycarbonyl or ethoxycarbonyl may be substituted, Benzimidazol-2-yl is represented by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, tert-butoxy, 2,4-dimethyl-3-pentoxy, methoxycarbonyl, di-isobutylamino -sulfonyl, tert-pentylaminosulfonyl, bis (hydroxyethyl) aminosulfonyl, morpholinosulfonyl, methoxyethoxypropylaminosulfonyl, nitro or cyano may be substituted, l, 3,4-thiadiazol-2-yl, which is 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 may be substituted,

Pyrrol-2-yl which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano and / or which has a - (CH ₂ ) in position 3,4 ₃ - or - (CH ₂ ) ₄ bridge and / or that in position 5 by hnino, dicyanomethylene, methoxycarbonyl-cyano-methylene, ethoxy-carbonyl-cyano-methylene or a radical of the formula (XH)

3-H-indolin-2-yl, which bears two methyl groups or an oxo group in position 3 and is substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl,

Methoxy, methoxycarbonyl, nitro or cyano can be substituted,

Isoindol-1-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano and / or in position 3 by imino, dicyanomethylene, methoxycarbonyl-cyano methylene, ethoxycarbonyl-cyano-methylene or a radical of the formula (XH)

wherein X is NR ⁵ and Y ¹ to Y ³ , R ⁴ , n and R ^{5 have} the meaning given above but are independent of it, can be substituted or l, 2,4-triazol-2-yl, which can be substituted by methyl or phenyl.

9. Optical data carrier according to at least one of claims 1 to 8, characterized in that the metal complexes used as light-absorbing compounds have at least one ligand of the formulas (I-A) to (I-ZA)

worm

A and B 'independently for

2-pyridyl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, nitro or cyano,

Benzthiazol-2-yl, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano may be substituted

Benzoxazol-2-yl, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentόxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano may be substituted Imidazol-2-yl, which can be substituted by up to two identical or different radicals from the series chlorine, methyl, methoxy, phenyl, cyano, -C (= NH) -OCH ₃ , nitro, methoxycarbonyl or ethoxycarbonyl,

Benzimidazol-2-yl, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano can be substituted, l, 3,4-thiadiazol-2-yl 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,

3-H-ldolin-2-yl which bears two methyl groups or one oxo group in position 3 and can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano .

Isoindol-1-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano and or in position 3 by I ino, dicyanomethylene, methoxycarbonyl cyano-methylene, ethoxycarbonyl-cyano-methylene may be substituted, or 1,2,4-triazol-2-yl, which may be substituted by methyl or phenyl,

A 'for pyridin-2-yl-6-ylidene, l, 3,4-triazol-2yl-5-ylidene, pyrrol-2yl-5-ylidene, 3,4-tetramethylenepyrrol-2yl-5-ylidene or optionally by fluorine , Chlorine, methyl, methoxy, methoxycarbonyl, nitro or cyano substituted isoindolyl-3-ylidene,

Quinolin-2-ylidene, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, nitro or cyano, 1,3-thiazol-2-yidene, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methoxy, phenyl or cyano,

Benzthiazol-2-ylidene, which is composed of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano may be substituted

Benzoxazol-2-ylidene, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano can be substituted

Imidazol-2-ylidene, which can be substituted by up to two identical or different radicals from the series chlorine, methyl, methoxy, phenyl, cyano, -C (= NH) -OCH ₃ , nitro, methoxycarbonyl or ethoxycarbonyl,

Benzimidazol-2-ylidene, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano may be substituted, l, 3,4-thiadiazol-2-ylidene by chlorine, bromine, methoxy, phenoxy, methanesulfonyl, methylthio, ethylthio, dimethylamino, diemylamino, 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 may be substituted,

Isoindole-1-ylidene, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano and / or which is in position 3 by imino, dicyanomethylene, methoxycarbonyl- cyano-methylene, ethoxycarbonyl-cyano-methylene may be substituted, or 1,2,4-triazol-2-ylidene, which may be substituted by methyl or phenyl,

R ¹ to R ⁴ independently of one another represent hydrogen, chlorine, methyl, benzyl, pyridylmethyl, phenyl, cyano, methoxycarbonyl or ethoxycarbonyl and R ² additionally represents methoxy, ethoxy, dimethylamino, diethylamino, pyrrolidino or piperidino or

R ^J ; R ² in formula (IH), (IJ), (1-0), (IP), (IU) to (I-ZA) together for an optionally substituted by methyl, phenyl and / or cyano bridge with the Atomic sequence -CR * = N-NR "-, - (C == 0) -NR" - (C = 0) -NR "'-, where R', R" and R "'independently of one another are H. , Alkyl, in particular Ci-C ^ alkyl preferably methyl or aryl, in particular Cg-Cio-aryl preferably phenyl, or

R *; R ² in formula (IE), (LP), (IH), (IJ), (IO), (IP), (IU) to (I-ZA) together for one - (CH ₂ ) ₃ - , - (CH ₂ ) ₄ - or -CH = CH-CH = CH-bridge and R ^{5 is} methyl, ethyl, by optionally up to two identical or different radicals of the series methyl, methoxy, chlorine, nitro, cyano, methylsulfonyl , Methoxycarbonyl, ethoxycarbonyl substituted phenyl-, 2-, 3- or 4-pyridyl-, 2-, 3- or 4-quinolyl-, thiazol-2-yl-, benzthiazol-2-yl-, benzoxazol-2-yl- , Imidazol-2-yl, benzimidazol-2-yl, l, 3,4-triazol-2-yl radicals, formyl, acetyl, trifluoroacetyl, acryloyl, methacryloyl, benzoyl, methylbenzoyl, chlorobenzoyl, methanesulfonyl, trifluoromethanesulfonulfonyl , Benzenesulfonyl, toluenesulfonyl, chlorobenzenesulfonyl, methoxycarbonyl, ethoxycarbonyl, N, N-dimethylcarbamoyl, N, N-dimethylsulfamoyl, N-2,2,2-trifluoroethylsulfamoyl, N-methyl-N-2,2,2-trifluoroethylsulfamoyl, pyridine -2-, 3- or 4-carbonyl, pyridine-2-, 3- or 4-sulfonyl or benzthiazole-2-sulfonyl,

Y ⁴ for = 0, = S or a remainder of the formulas

R '(XH!) Or Π CMN

stands,

R ^{6 represents} hydrogen, phenyl, cyano, methoxycarbonyl or ethoxycarbonyl

and

R ^{7 represents} hydrogen, methyl, ethyl, phenyl, tolyl, chlorophenyl, anisyl, 2-pyridyl, thiazol-2-yl or benzthiazol-2-yl.

0. Optical data carrier according to at least one of claims 1 to 9, characterized in that the metal complexes used as light-absorbing compounds have at least one ligand of the formulas (I-A) or (I-B)

wherein

A represents a 2-pyridyl, l, 3-thiazol-2-yl, benzothiazol-2-yl or benzoxazol-2-yl radical which is represented by -0-CH ₂ -CH (CH ₃ ) ₂ , -0-CH [CH (CH ₃ ) ₂ ] ₂ , -0-C (CH ₃ ) ₃ , -O-CH ₂ -CH (C ₂ H ₅ ) (C ₄ H ₉ ), -0-CH ₂ - C (CH3) ₂ -C ₂ H5, -S0 ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -COOCH ₂ CH ₃ , -S0 ₂ NHCH ₂ CH (CH ₃ ) ₂ , -S0 ₂ NHC (CH ₃ ) ₂ CH ₂ CH ₃ , -S0 ₂ NHC (CH ₃ ) ₃ , -CH ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -S0 ₂ NH- (CH ₂ CH ₂ CH ₂ 0-) ₂ CH ₃ , -S0 ₂ NH- (CH ₂ CH ₂ CH ₂ 0) - (CH ₂ CH ₂ 0) -CH ₃ , -S0 ₂ N (CH ₂ CHOH) ₂ , SO ₂ N (CH ₂ CH (CH ₃ ) CH ₂ OH) ₂

and / or is substituted,

B represents a pyridin-2-ylidene, 1,3-thiazol-2-ylidene, benzothiazol-2-ylidene or benzoxazoliden-2-yl radical which is replaced by hydrogen, -O-CH ₂ -CH (CH ₃ ) ₂ , -0-CH [CH (CH ₃ ) ₂ ] ₂ , -0-C (CH ₃ ) ₃ , -0-CH ₂ -CH (C ₂ H ₅ ) (C ₄ H ₉ ), -0 -CH2-C (CH ₃ ) ₂ -C ₂ H ₃ , -SO ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -COOCH ₂ CH ₃ , -S0 ₂ NHCH ₂ CH (CH ₃ ) ₂ , - SO ₂ NHC (CH ₃ ) ₂ CH ₂ CH ₃ , -S0 ₂ NHC (CH ₃ ) ₃ , -CH ₂ N (CH ₂ CH (CH ₃ ) ₂ ) ₂ , -SO ₂ NH- (CH ₂ CH ₂ CH ₂ O-) ₂ CH ₃ , -SO ₂ NH- (CH ₂ CH ₂ CH ₂ 0) - (CH ₂ CH ₂ 0) -CH ₃ , -SO ₂ N (CH ₂ CHOH) ₂ , S0 ₂ N (CH ₂ CH (CH ₃ ) CH ₂ OH) _2j

is substituted.

11. Optical data carrier according to at least one of claims 1 to 9, characterized in that the metal complexes used as light-absorbing compounds have at least one ligand of formein (I-C)

wherein

B for a pyridin-2-ylidene, l, 3-thiazol-2-ylidene or benzothiazol-2-ylidene residue which may be substituted by chlorine, methyl, methoxy, cyano or methoxycarbonyl, l, 3,4- Thiadiazol-2-ylidene radical, which may be substituted by methylthio, dimethylamino, diethylamino, diisopropylamino, pyrrolidino or morpholino, or 1,3,4-triazol-2-ylidene radical.

12. Optical data carrier according to at least one of claims 1 to 9, characterized in that the metal complexes used as light-absorbing compounds have at least one ligand of the formulas (I-G), (I-H) or (I-J)

wherein

R ^{1 represents} hydrogen, phenyl or cyano,

R ^{2 represents} hydrogen or

R *; R ² stand for a -CH = CH-CH = CH bridge,

R ^{5 is} phenyl, tolyl, chorphenyl, nitrophenyl, 2-, 3- or 4-pyridyl, thiazol-2-yl, benzthiazol-2-yl, trifluoroacetyl, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, cyanobenzenesulfonyl, N, N-dimethylsulfamoyl -2-, 3- or 4-sulfonyl,

or have at least one ligand of formula (I-K) or (I-Q)

wherein

Y ^{4 stands} for = 0, = S, = NH or = C (CN) ₂ , A 'for 3,4-tetramethylene pyrrol-2-yl-5-ylidene, a pyrrol-2-yl-5-ylidene or isoindol-l-yl-3-ylidene residue, which is represented by methyl, methoxy, nitro or can be substituted cyano,

B 'represents a 2-pyridyl, 2-quinolyl, 1,3-thiazol-2yI, benzthiazol-2-yl, benzoxazol-2-yl or 3,3-dimethylindolin-2-yl radical, which can be substituted by methyl, methoxy, chlorine, cyano or methoxycarbonyl,

B for a pyridin-2-ylidene, quinolin-2-ylidene, 1,3-thiazol-2ylidene, benzothiazol-2-ylidene, benzoxazol-2-ylidene or 3,3-dimethylindolin-2-ylidene Radical which can be substituted by methyl, methoxy, chlorine, cyano or methoxycarbonyl, or at least one ligand of the formula (IL) or (IR)

wherein

Y ^{4 stands} for = O, = S, = NH or = C (CN) ₂ ,

A 'for 3,4-tetramethylene-pyrrol-2-yl-5-ylidene, a pyrrol-2-yl-5-ylidene or isoindol-l-yl-3-ylidene residue, which is represented by methyl, methoxy, nitro or can be substituted cyano,

B 'for a 2-pyridyl, 2-pyrimidyl, l, 3-thiazol-2yl, benzthiazol-2-yl, benzoxazol-2-yl radical, which is represented by methyl, methoxy, chlorine, cyano or Methoxycarbonyl may be substituted, 1,3,4-triazol-2-yl or 1,3,4-thiadiazol-2-yl radical which can be substituted by dimethylamino, diethylamino, diisopropylamino, pyrrolidino or morpholino,

B for a pyridin-2-ylidene, pyrimidin-2-ylidene, l, 3-thiazol-2ylidene, benzothiazol-2-ylidene, benzoxazol-2-ylidene residue, which is characterized by methyl, methoxy, chlorine . Cyano or methoxycarbonyl can be substituted, l, 3,4-triazol-2-ylidene or a l, 3,4-thiadiazol-2-ylidene radical which can be substituted by dimethylamino, diethylamino, diisopropylamino, pyrrolidino or morpholino , or have at least one ligand of the formula (IO) or (IU)

(IN),

wherein

Y ^{4 stands} for = 0, = S, = ΝH or = C (CΝ) ₂ ,

R ^{1 represents} hydrogen,

R represents dimethylamino, diemylane, pyrrolidino or piperidino or

R ^X ; R stand for a -CH = CH-CH = CH bridge,

or have at least one ligand of the formula (I-W)

wherein A 'for 3,4-tetramethylene-pyrrol-2-yl-5-ylidene, a pyrrol-2-yl-5-ylidene or isoindol-l-yl-3-ylidene residue, which is represented by methyl, methoxy, nitro or can be substituted cyano,

R ^{1 represents} hydrogen or cyano, R ^{2 represents} methoxy, ethoxy, dimethylamino, diethylamino, pyrrolidino or piperidino,

B for a pyridin-2-ylidene, quinolin-2-ylidene, 1,3-thiazol-2ylidene, benzothiazol-2-ylidene, benzoxazol-2-ylidene or 3,3-dimethylindolin-2-ylidene Radical which can be substituted by methyl, methoxy, chlorine, cyano or methoxycarbonyl, or have at least one ligand of the formula (IX)

worm

R ^{1 represents} hydrogen or cyano,

R ^{2 represents} methoxy, ethoxy, dimethylamino, diethylamino, pyrrolidino or piperidino, B represents a pyridin-2-ylidene, pyrimidin-2-ylidene, 1,3-thiazol-2ylidene, benzothiazol-2-ylidene , Benzoxazol-2-ylidene radical, which can be substituted by methyl, methoxy, chlorine, cyano or methoxycarbonyl, l, 3,4-triazol-2-ylidene or a l, 3,4-thiadiazol-2-ylidene radical , which can be substituted by dimethylamino, diethylamino, diisopropylamino, pyrrolidino or morpholino.

13. Optical data carrier according to at least one of claims 1 to 8, characterized in that the metal complexes used as the light-absorbing compound at least one of the formulas (HA) to (HK), (HQ) to (LI-N), (QT-K) to (ELT-P) and (DI-W) to (HI-ZA) correspond

(Π-J),

(Π-v),

have meaning given in one of claims 1 to 8.

14. A method for producing an optical data carrier according to at least one of claims 1 to 13, characterized in that a preferably transparent, possibly already coated with a reflection and / or protective layer substrate with at least one metal complex as a light-absorbing compound, the at least one ligand Formula (!), Optionally coated in combination with suitable binders and additives and optionally solvents and optionally provided with a reflection layer, further intermediate layers and optionally a protective layer or another substrate or a covering layer.

15. Metal complexes which have at least one ligand of the formula (I)

have, wherein the rest of the formula

for -N = N-, -CR ^! = N-, -CR ^ CR ² -, -N = CR ² -, -N = NN = CR ⁴ -, -CR ¹ = CR ² -N = CR ⁴ - or -CR ¹ = CR ² -CR ³ = CR ⁴ - stands.

16. Metal complexes according to claim 15, characterized in that they have at least one ligand of the formula (I-A) to (I-ZA)

wherein

Benzthiazol-2-yl, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano can be substituted, benzoxazol-2-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl , Methoxycarbonyl, nitro or cyano can be substituted,

Imidazol-2-yl, which can be substituted by up to two identical or different radicals from the series chloro ^ methyl, methoxy, phenyl, cyano, -C (= NH) -OCH ₃ , nitro, methoxycarbonyl or ethoxycarbonyl,

Benzimidazol-2-yl, which is composed of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, Di-isobutylaminosulfonyl, methoxycarbonyl, nitro or cyano 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-cyanoethylamino, N, N-biscyanethylamino, N-methyl-N-hydroxyethylamino, N-methyl-N-benzylamino, N-methyl-N-phenylamino, anilino, pyrrolidino, piperidino or morpholino can be substituted,

Isoindol-1-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano and / or which is in position 3 by hnino, dicyanomethylene, methoxycarbonyl cyano-methylene, ethoxycarbonyl-cyano-methylene may be substituted, or 1,2,4-triazol-2-yl, which may be substituted by methyl or phenyl,

A 'for pyridin-2-yl-6-ylidene, l, 3,4-triazol-2yl-5-ylidene, pyrrol-2yl-5-ylidene, 3,4-' partramethylene-pyrrol-2yl-5-ylidene or optionally by Fluorine, chlorine, methyl, methoxy, methoxycarbonyl, nitro or cyano substituted isoindolyl-3-ylidene,

Benzthiazol-2-ylidene, which is composed of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3- pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or cyano may be substituted,

Benzoxazol-2-ylidene, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano may be substituted

Lτnidazol-2-ylidene, which can be substituted by up to two identical or different radicals from the series chlorine, methyl, methoxy, phenyl, cyano, -C (= NH) -OCH ₃ , nitro, methoxycarbonyl or ethoxycarbonyl, benzimidazole-2 -ylidene, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or cyano can, l, 3,4-thiadiazol-2-ylidene 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,

Isoindole-1-ylidene, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano and or in position 3 by imino, dicyanomethylene, methoxycarbonyl-cyano-methylene , Ethoxycarbonyl-cyano-methylene can be substituted, or l, 2,4-triazol-2-ylidene which can be substituted by methyl or phenyl,

R ² additionally represents methoxy, ethoxy, dimethylamino, diethylamino, pyrrolidino or piperidino or R ^J ; R ² in formula (IH), (IJ), (IO), (IP), (IU) to (I-ZA) together for a bridge optionally substituted by methyl, phenyl and / or cyano with the atomic sequence - C = NN-, - (C = 0) -N- (C = 0) -N- or

R ^! ; R ² in formula (IE), (IF), (IH), (IJ), (IO), (IP), (IU) to (I-ZA) together for one - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ - or -CH = CH-CH = CH bridge and

R ^{5 is} methyl, ethyl, phenyl-, 2-, 3- or 4-pyridyl-, 2-, optionally substituted by up to two identical or different radicals from the series methyl, methoxy, chlorine, nitro, cyano, methylsuifonyl, methoxycarbonyl, ethoxycarbonyl , 3- or 4-quinolyl-, thiazol-2-yl-, benzthiazol-2-yl-, benzoxazol-2-yl-, imidazol-2-yl-, benzimidazol-2-yl-, l, 3,4- Triazol-2-yl radicals, formyl, acetyl, trifluoroacetyl, acryloyl, metacryloyl, benzoyl, methylbenzoyl, chlorobenzoyl, methanesulfonyl, trifluoromethanesulfonyl, perfluorobutanesulfonyl, benzenesulfonyl, toluenesulfonyl, methoxycarbonyl nylcarbonyl, ethoxycarbonyl nylcarbonylamyl, methoxycarbonyl nylcarbonylamyl, methoxycarbonyl nylcarbonyl, methoxycarbonyl nyl, methoxycarbonyl nyl, methylbenzoyl carbonyl N-dimethylsulfamoyl, N-2,2,2-trifluoroethylsulfamoyl, N-methyl-N-2,2,2-trifluoroethylsulfamoyl, pyridine-2-, 3- or 4-carbonyl, pyridine-2-, 3- or 4- sulfonyl or benzthiazole-2-sulfonyl,

Y ⁴ for = 0, = S or a remainder of the formulas

(XHI) or r C.MN

^ R ⁷ (XIV) stands,

R ^{δ represents} hydrogen, phenyl, cyano, methoxycarbonyl or ethoxycarbonyl and

17. Metal complexes according to at least one of claims 15 to 16, characterized in that they have the formulas (HA) to (HJ), (HQ) to (HV), (HI-K) to (JE-?) And (TH- W) to (HI-ZA).

(N-τ),

where M, An and the residues of the respective ligands independently of one another have the abovementioned meaning.

18. Solution containing a) at least one metal complex according to at least one of claims 15 to 17 and b) at least one organic solvent.

19. Solution according to claim 18 containing as organic solvent of component b) at least solvent from the group 2,2,3,3-tetrafluoropropanol, propanol, butanol, pentanol, hexanol, diacetone alcohol, dibutyl ether, heptanone or mixtures thereof.

20. A process for the preparation of metal complexes according to at least one of claims 15 to 17, characterized in that a metal salt with a ligand compound of the formula)

in which A represents an optionally substituted and / or benzyl or naphthane-fused five- or six-membered aromatic or quasi-aromatic or partially hydrogenated heterocyclic radical, n represents 0 or 1,

Y ^{1 represents} N or CR ¹ , Y ^{2 represents} N or CR ² ,

Y ^{3 represents} N or CR ³ ,

X represents O, S or NR ⁵ ,

R ^{5 represents} hydrogen, alkyl, alkenyl, aralkyl, cycloalkyl, acyl, aryl or a heterocyclic radical, R ¹ to R ⁴ independently of one another represent hydrogen, halogen, alkyl, alkoxy, mono- or dialkylamino, aralkyl, aryl, hetaryl, arylazo , Hetarylazo, cyano or alkoxycarbonyl,

R ^! R ^{2 can form} an optionally substituted and / or optionally containing triatomic bridge or an optionally substituted four-atom bridge which contains no or at least 2 heteroatoms,

R; R ³ and R ⁴ ; R ⁵ can each independently form a bridge and R ² ; R ⁵ can form a bridge when n is 0 and in which the rest of the formula

for -N = N-, -CR.MN-, -CR ^ CR ¹ -, -N = CR ² -, -N = NN = CR ⁴ -, -CR ¹ = CR ² -N = CR ⁴ - or - CR ^ CR ^ CR ^ CR ⁴ -, stands, implements.

21. Use of the metal complexes according to at least one of claims 15 to 17 as a light-absorbing compound in the information layer of write-once optical data carriers which can be written and read with light having a wavelength in the range from 360 to 460 nm.

22. Ligand compound of the formula (Id)

wor

A represents an optionally substituted and / or benzyl or naphthane-fused five- or six-membered aromatic or quasi-aromatic or partially hydrogenated heterocyclic radical, n represents 0 or 1,

Y ^{1 represents} N or CR ¹ ,

Y ^{2 represents} N or CR ² ,

Y ^{3 represents} N or CR ³ , X represents O, S or NR ⁵ ,

R ^ R ^{2 can form} an optionally substituted and / or optionally containing heteroatoms triatomic bridge or an optionally substituted fouratoms bridge which contains no or at least 2 heteroatoms,

R ² ; R ³ and R ⁴ ; R ⁵ can each independently form a bridge and

R ² ; R ⁵ can form a bridge when n is 0 and in which the rest of the formula

for -N = N-, -CR ^ N-, -CR ^ CR ¹ -, -N = CR ² -, -N = NN = CR ⁴ -, -CR ^J = CR ² -N = CR ⁴ - or - CR ^ CR ^ CR ^ CR ⁴ - stands.

23. Ligand compound according to claim 22, characterized in that they correspond to the protonated form of at least one formula (I-A) to (I-ZA).

wherein

A and B 'independently for 2-pyridyl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, nitro or cyano,

Benzoxazol-2-yl, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano may be substituted

Imidazol-2-yl, which consists of up to two identical or different radicals from the

Series chlorine, methyl, methoxy, phenyl, cyano, -C (HNH) -OCH ₃ , nitro, methoxycarbonyl or ethoxycarbonyl may be substituted,

Benzimidazol-2-yl, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano may 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-cyanoethylamino, N, N-biscyanethylamino, N-methyl-N-hydroxyethylamino, N-methyl-N-benzylamino, N-memyl-N-phenylamino, anilino, pyrrolidino,

Piperidino or morpholino can be substituted,

3-H-indolin-2-yl which bears two methyl groups or one oxo group in position 3 and can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano . Isoindol-1-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano and / or which is in position 3 by imino, dicyanomethylene, methoxycarbonyl-cyano- methylene, ethoxycarbonyl-cyano-methylene can be substituted, or l, 2,4-triazol-2-yl, which can be substituted by methyl or phenyl,

Benzoxazol-2-ylidene, which consists of up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3-pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or Cyano can be substituted, imidazol-2-ylidene, which can be substituted by up to two identical or different radicals from the series chlorine, methyl, methoxy, phenyl, cyano, -C (-NH) -OCH ₃ , nitro, methoxycarbonyl or ethoxycarbonyl can

Benzimidazol-2-ylidene, which is substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, ethoxy, isobutoxy, 2,4-dimethyl-3- pentoxy, di-isobutylaminosulfonyl, methoxycarbonyl, nitro or cyano may be substituted, l, 3,4-thiadiazol-2-ylidene 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 may be substituted,

Isoindol-1-ylidene which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, methoxy, methoxycarbonyl, nitro or cyano and / or which is in position 3 by Lnino, dicyanomethylene, methoxycarbonyl cyano-methylene, ethoxycarbonyl-cyano-methylene may be substituted, or 1,2,4-triazol-2-ylidene, which may be substituted by methyl or phenyl,

R ² additionally represents methoxy, ethoxy, dimethylamino, diethylamino, pynolidino or piperidino or

R; R ² in formula (IH), (IJ), α ~ O), Q - P), (IU) to α- A) together for a bridge with the atom which is optionally substituted by methyl, phenyl and / or cyano - follow -C = NN-, - (C = 0) -N- (C = 0) -N- or

R ^J ; R ² in formula (EE), (IF), (1-ΕJ), (IJ), (lO), (IP), (IU) to (I-ZA) together for one - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ - or -CH = CH-CH = CH-bridge and

R ^{5 is} methyl, ethyl, phenyl-, 2-, 3- or 4-pyridyl-, optionally substituted by up to two identical or different radicals from the series methyl, methoxy, chlorine, nitro, cyano, methylsulfonyl, methoxycarbonyl, ethoxycarbonyl, 2-, 3- or 4-quinolyl-, thiazol-2-yl-, benzthiazol-2-yl-, benzoxazol-2-yl-, imidazol-2-yl-, benzimidazol-2-yl-, 1,3, 4-triazol-2-yl residues, formyl, acetyl, trifluoroacetyl, acryloyl, metacryloyl, benzoyl, methylbenzoyl, chlorobenzoyl, methanesulfonyl, trifluoromethanesulfonyl, perfluorobutanesulfonyl, benzenesulfonyl, toluenesulfonyl, nethoxycarbonyl-sulfonyl, chlorobenzoyloxy-carbonyl, chlorobenzoyloxy-carbonyl N, N-dimethylsulfamoyl, N-2,2,2-trifluoroethylsulfamoyl, N-methyl-N- 2,2,2-trifluoroethylsulfamoyl, pyridine-2-, 3- or 4-carbonyl, pyridine-2-, 3- or 4-sulfonyl or benzothiazole-2-sulfonyl,

Y ⁴ for = 0, = S or a remainder of the formulas

^ -R ⁷ (XTV) stands,

R ^{6 represents} hydrogen, phenyl, cyano, methoxycarbonyl or ethoxycarbonyl and

24. Optical data carriers according to at least one of claims 1 to 13 described with light of the wavelength 360-460 nm, in particular with laser light.