DE19738822A1 - Transition metal oxoporphine derivatives useful e.g. as pigment, photosensitizer or catalyst - Google Patents

Abstract

Transition metal oxoporphine derivatives (I), in which each pyrrole ring has a condensed aromatic ring, at least one of which contains hetero-atom(s), all their isomers, stereoisomers, enantiomers and diastereomers and all their mu -oxo-dimers and mu -oxo-oligomers are new. The oxoporphine derivatives are of formula (I); M = a transition metal; X<1-4> = a nitrogen (N) atom or a carbon (C) atom, optionally substituted by R; q = the total charge; n = 1 or 2; A<1-4> = condensed aromatic rings, at least one of which contains ring heteroatom(s). An Independent claim is also included for the preparation of (I).

Description

The invention relates to substituted and unsubstituted ized transition metal oxoporphins and transition metal oxomono-, di, tri and tetraazaporphins including all isomers, Stereoisomers or enantiomers and diastereomers and all their µ-oxo dimers and µ-oxo oligomers, their representation and their use as pigments for light filter glasses, as La water dyes, as photosensitizers, as direct dyes in photography, as selective catalysts for Reductions and oxidations, in photovoltaics, in opto electronics as materials for information storage, as ion selective ion carrier and optode materials, as NMR shift reagents, as liquid crystals and as generators of carbenes and singlet oxygen.

As pigments for light filter glasses, as laser dyes, as photosensitizers, as catalysts, in optoelec electronics as materials for information storage, as selek tive catalysts for reductions and oxidations and as Er producers of carbenes and singlet oxygen relatives so far Dyes are characterized by a too low for these purposes lightfastness, often show poor solubility behavior, generally low chemical stability and often extinction coefficients much too low. So far for that  related porphins and azaporphines are also often in only moderate yields, with great effort and expensive educ can be displayed.

Transition metal oxoporphins are for example in the EP 0 337 209 B1 described, which as an absorbent in near IR can be used.

The invention has for its object in good yields available, readily soluble compounds are available len, which have high light fastness, chemical stability as well have high extinction coefficients.

The object is finally achieved by the compounds according to claim 1 including all of their isomers and also µ-oxo dimers and µ-oxo oligomers, the monomers being represented by the following structure, where at least one of the rings A ¹ -A ^{4 is} at least one has a hetero atom,

where X ^1-4 = N and / or CR ¹ , CR ² , CR ³ , CR ⁴ (independently of one another) and where M represents a transition metal. The total charge q of the non-bridged transition metal oxoporphine derivatives is

q = z - 2n - 2 + q _A1 + q _A2 + q _A3 + q _A4

where z is the oxidation state of the transition metal in question, n is the number of oxo groups and q _A1 , q _A2 , q _A3 and q _{A4 are} the charges of the different or identical aromatic condensates A ¹ to A ⁴ ; the charge of the µ-oxo dimers and µ-oxo oligomers results accordingly. The ge ions for q not equal to 0 can be common organic or organic ions.

Advantageous derivatives can be found in subclaims 2 to 5 to take. The invention relates to all substit ized and unsubstituted transition metal oxoporphine or -mono-, -di, -tri- or -tetraazaporphinderivate as well as all de ren isomers, stereoisomers or enantiomers and diastereomers.

The condensed aromatic substituents A ¹ -A ⁴ can be different or identical and are preferably selected from the group:

The substituents C ¹ , C ² are cyclic or polycyclic systems, fused aryl and heteroaryl radicals with any number of substituents R, where the substituents R can also be different.

The substituents R (R ¹ to R ⁸ ) of the A ¹ -A ⁴ , C ¹ , C ² radicals and for X ^1-4 = CR (R = R ¹ to R ⁴ ) are selected independently of one another from up to the group:
-H; Alkyl; Alkenyl; Alkynyl; Cycloalkyl; Cycloalkenyl; Cycloalkynyl; Aryl, heteroaryl, metallocenyl; -SiR ₃ ; -CO-R; -CS-R; -CNR-R; -CNR ₂ ⁺-R; -COO⁻; -COOR; -COS⁻; -COSR; -CSS⁻; CSSR; -CONR ₂ ; -CNR-NR ₂ ; -CNR ₂ ⁺-NR ₂ ; -CN; -CN⁺-R; -NC; -NR ₂ ; -NR ₃ ⁺; -NR-NR ₂ , -N ₂ R ₄ ⁺; -N ₂ ⁺; -N = NR; -N ₂ R ₂ ⁺; -NO, -NO ₂ ; -PR ₂ ; -PR ₃ ⁺; -PO ₂ R⁻; -PO ₂ R ₂ ; -POSR⁻; -POSR ₂ ; -PS ₂ R⁻; -PS ₂ R ² ⁻; -PO ₃ ² ⁻; -PO ₃ R⁻; -PO ₃ R ₂ ; -PO ₂ S ² ⁻; -PO ₂ SR⁻; -PO ₂ SR ₂ ; -POS ₂ ² ⁻; -POS ₂ R⁻; -POS ₂ R ₂ ; -PS ₃ ² ⁻; -PS ₃ R⁻; -PS ₃ R ₂ ; -Oxo; -OR; -S⁻; -SR; -S ₂ ⁻; -S ₂ -R; -SO-R; -SO ₃ ⁻; -SO ₃ -R; -SO-NR ₂ ; -SONR ₃ ⁺; -SO ₂ -NR ₂ ; -SO ₂ NR ₃ ⁺; -Halo gen; -IO; -IR ₂ ; -SCN, -OCN; -NCS; -NCO; -BR ₂ ; -BR ₃ -; -O-BR ₂ , where the alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl and metallocenyl radicals are in turn mono- or polysubstituted with R = R ¹ to R ⁸ and R ¹ to R ⁸ can be identical or different.

In particular Metalloxoporphine and Metalloxotetraazaporphine distinguished by high light fastness and chemical Bestän of speed, when the transition metal M is selected from the group Ti, Zr. In particular, porphine and Tetraazaporphin- compounds with tetravalent ring fabric nitrogen atoms of the A ¹ -A ⁴ substituents are Hf to be used advantageously, in particular when M = Ti. The number and arrangement of the ring heteroatoms make it possible to adjust the properties of the porphine derivatives, in particular their tendency to aggregate in solution.

The metal oxoporphins described here (X = independently of one another CR ¹ , CR ² , CR ³ or CR ⁴ ) can, for. B. from the following isoindolimine analogs and corresponding metal compounds (transition metal preferably Ti, Zr, Hf) in high-boiling, inert solvents, such as DMAE or higher alcohols such as absolute pentanol, in boiling heat under protective gas and subsequent hydrolysis.

(R = R ¹ , R ² , R ³ or R ⁴ identical or independent of each other).

The metal oxotetraazaporphins described here (X = N) are those of the following dinitriles and corresponding metal compounds (metal preferably Ti, Zr, Hf) in likewise high-boiling, inert solvents, such as, for example, DMAE or higher alcohols in boiling heat under protective gas and subsequent hydrolysis shown:

The mono-, di-, triaza connections are made accordingly bar. The manufacturing process shown has especially for the production of Ti, Zr and Hf compounds proven that otherwise tend to decompose.

The transition metal oxoporphine derivatives or their µ-oxo dimers and µ-oxo oligomers with M = Cr, Mo, Mn, Fe, Ru, Os, Rh and Ir are based on an analogous process with transition metal compound preferably low transition metal oxidation level representable. The transfer of the com plexed transition metal ions of one of the invention Transition metal oxoporphine derivatives in a higher or lower gere oxidation stage can by electrolysis or by a suitable oxidizing or reducing agent. The Formation of the µ-oxo dimers or oligomers from the monomers follows, if necessary in the presence of oxygen, under übli conditions.

The compounds of the invention are in particular as pig elements for light filter glasses, as laser dyes, as photos sensitizers, as direct color developers in the photogra phie, as selective catalysts for reductions and oxides ions, in photovoltaics, in optoelectronics as mate  rialien for information storage, as ion-selective ions carrier and optode materials, as NMR shift reagents cien, as liquid crystals and as a producer of carbenes and Singlet oxygen can be used.

The metal oxoporphins described here, especially with M = Ti, Zr, Hf, show high photoinstability compared to Organohalogen compounds, which is why they are used for the production of grainless photographic films and images can be used can without the addition of silver halides necessary is. Such grainless photographic films and pictures draw are characterized by exceptional sharpness and contrast.

When irradiated with UV / Vis radiation, the be wrote Metalloxoporhine depending on the oxidation level of Zen tralkations a charge transfer from the ligand to the metal oxo- Central cation. This intramolecular photolytic charge separation can be used to manufacture solar cells the. Because of the near-infrared absorption, it is much larger Outer wavelength range for photolytic charge separation accessible than this with ordinary silicon or copper sulfide solar cells in photovoltaics is possible. Furthermore the manufacturing process of such metal oxopor is designed phin solar cells by immersion and evaporation from por phin solutions far easier than the previous production of Silicon or copper sulfide solar cells. Also a manufacture by vacuum sublimation of the porphine is possible.

Due to the intramolecular photolytic charge separation can with the metal oxoporphins and described here Metalloxotetraazaporphinen very easily the photochemical Oxidation and reduction properties vary. You can hence by irradiation as an electron transfer catalyst be used in analogy to natural photosynthesis. The catalytic reactions are advantageously such carried out that a solution containing a Me contains talloxoporphin derivative and a substrate with a  Oxidizing agent or a reducing agent with or without Light irradiation is converted into a product. The invent Compounds according to the invention are also advantageous as antistatic agents usable.

The compounds of the invention can be used to prepare Light filter glasses are used. The Me talloxoporphine derivatives are dissolved in a monomer solution, whereupon a polymerization is subsequently carried out, so that the porphine derivatives are distributed in a polymeric matrix are. Alternatively, a copolymerization of the inventions is also possible porphine derivatives according to the invention with monomers to a suitable Polymer possible. Furthermore, the invention Compounds dissolved or suspended in a polymer solution are, after which the solvent is evaporated.

For the production of optical recording media under Ver using the porphine derivatives according to the invention can be a Porphin derivative containing solution applied to a substrate be, with evaporation of the solvent on drawing layer is formed.

The metal oxoporphins described here are strong oxophiles Lewis acids, which is why they are preferred as M = Ti, Zr, Hf almost exclusive hydroxide-selective ion carrier in OK nenselective electrodes can be used. Since the ent speaking hydroxide complexes against their absorption behavior change over UV / Vis radiation, they can be used as materials use for optodes. By choosing the transition metals and Choice of oxidation levels with M = Cr, Mo, Mn, Fe, Ru, Os, Rh, and Ir the selectivities for other anions, e.g. B. set for halides.

Because of the special oxophilic Lewis acidity and the ring current effect of the corresponding aromatic porphine ligands and the porphine ring itself can be described here  Metal oxoporphins preferably with M = Ti, Zr, Hf as very star ke NMR shift reagents are used. As ver shifter reagents or catalysts can also be chiral Porphine derivatives with enantioselective properties are used become.

The metal oxoporphins described here show a strong one Tendency to aggregate if not determined by certain sub is suppressed. Are z. B. long alkyl substituents introduced, such metal show oxoporphine liquid crystalline properties and are suitable as excellent due to their optical properties as Materials for LCD applications. Furthermore, they are up due to their electronic properties in a suitable matrix and applicable as a solid in nonlinear optics.

Because of the diverse and specifically variable properties There is a wide range of applications for the be wrote metal oxoporphins compared to other porphin descendants and other materials.

The following examples serve to explain the invention further:
The titanium (+ IV) oxotetrapyrido [2,3-h: 2 ', 3'-g: 2 ", 3" - 1: 2 "", 3 "" - q] tetraazaporphyrazine 2 (consisting of C _2V , C _S , C ₁ * and C ₄ * isomers) can be prepared very simply in anhydrous high-boiling solvent by reacting 2,3-dicyanopyridine 1 with titanium compounds under reflux:

560 mg (0.00434 mol) 1 were under N ₂ protective gas in a reflux apparatus in 25 ml abs. DMAE dissolved and slowly heated to 100 ° C in 0.5 h. Then 3 ml of titanium (+ IV) acid tetra-n-butyl ester were added and the mixture was heated further at 130 ° C. Two further additions of 3 ml each of titanium (IV) tetra-n-butyl ester followed at an interval of 1 h and the reaction was stopped after a total of 4 h after 2 h after the first addition of titanium (IV) tetra-n-butyl ester the characteristic blue color appeared.

After cooling to room temperature, the reaction mixture transferred to a centrifuge tube and first with water, then washed with acetone and then with chloroform for so long and centrifuged until only the blue reaction pro product and there was a yellowish supernatant in the centrifuge glass. For further purification, the crude product was left for six hours  subjected to Soxlett extraction with acetone until Ab flow solution no more yellowing occurred. Most recently that was deep blue product air-dried for two days. A Purification of the 1.30 g substance obtained can by sublime tion at 450 ° C in a vacuum.

2 is readily soluble in glacial acetic acid and decomplexation only occurs after about a week. Its UV spectrum is characteristic in this acidic medium ( Fig. 1); the absorption maxima are at the following wavelengths:
Q band: 654.0 nm
594.5 nm
B band: 328.0 nm.

A further reliable identification of 2 can be made via the TiO valence vibrations at 900 cm⁻ ¹ and via the framework vibrations at 1600-1050 cm⁻ ¹ in the IR spectrum.

In a further embodiment, compound 2 is reacted with a methylating agent; this is how N-methylated macrocycle 3 is created:

1.10 g 2 were suspended under N ₂ protective gas in 25 ml dichloromethane and jwls. Spatula tips trimethyloxonium tetra fluoroborate added at intervals of 12 h; the reaction was maintained with vigorous stirring for a week, but can be considered complete after 5 hours.

The suspension was then transferred to centrifuge tubes leads and cleaned intensively with dichloromethane. It was done drying the blue product over calcium chloride in Va vacuum at room temperature, with 1.68 g of a very hygroscopic blue powder was obtained. A cleaning can be done with Reversed phase column chromatography.

As the UV spectrum ( Fig. 2) shows, 3 is readily soluble in polar media.

The isomers of 3 could be distinguished with certainty in the ¹ H-NMR spectrum (250 MHz), DMSO-d ₆ being used as the NMR solvent:

The statistical mixture of isomers consisting of macrocycle 3 decays in a solution of 80% methanol and 20% dichloromethane under UV / Vis radiation under these conditions according to a first-order time law ( Fig. 3); the decay rate constant is approximately k = -2.2.10⁻ ⁴ s⁻ ¹ . Therefore, 3 can be used to make photographic images and films as an alternative to silver halides. For this purpose, application is carried out from a solution on a corresponding carrier 3 by means of immersion and evaporation technology. Another transparent layer, which contains, among other things, an organohalogen compound and is applied in the same way, is carried out over this layer. When exposed, 3 decays and a latent image is formed, which can be fixed by washing out the organohalogen compound with a solvent.

Claims (20)

1. Transition metal oxoporphine derivatives represented by the following structural formula
are shown in which M is a transition metal, X ^1-4 independently of one another either an N atom or an unsubstituted or substituted with a radical R and q is the total charge and where n is the number 1 or 2 and A ¹ - A ^{4 is} different or identical ankonden based aromatic rings, at least one of which has one or more ring heteroatoms, and all of their isomers, stereoisomers or enantiomers and diastereomers and all of their μ-oxo dimers and μ-oxo-oligo mers. 2. transition metal oxoporphine derivatives according to claim 1, wherein the condensed aromatics A ¹ -A ⁴ contain at least one nitrogen atom in the ring. 3. transition metal oxoporphine derivatives according to claim 1 or 2, wherein the condensed aromatics A ¹ -A ^{4 are} unsubstituted or mono- or polysubstituted with a radical R = R ⁵ -R ⁸ and are independently selected from the group:
where C ¹ , C ^{2 can represent} cyclic and polycyclic, fused aryl or heteroaryl radicals with any number of substituents R and where one or more X ^1-4 = CR (R ¹ -R ⁴ ), R = R ¹ to R ⁸ each independently a remainder is from the group:
-H; -Alkyl; Alkenyl; Alkynyl; Cycloalkyl; Cycloalkenyl; Cycloalkynyl; Aryl, heteroaryl, metallocenyl; -SiR ₃ ; -CO-R; -CS-R; -CNR-R; -CNR ₂ ⁺-R; -COO⁻; -COOR; -COS⁻; -COSR; -CSS⁻; CSSR; -CONR ₂ ; -CNR-NR ₂ ; -CNR ₂ ⁺-NR ₂ ; -CN; -CN⁺-R; -NC; -NR ₂ ; -NR ₃ ⁺; -NR-NR ₂ , -N ₂ R ₄ ⁺; -N ₂ ⁺; -N = NR; -N ₂ R ₂ ⁺; -NO, -NO ₂ ; -PR ₂ ; PR ₃ ⁺; -PO ₂ R⁻; -PO ₂ R ₂ ; -POSR⁻; -POSR ₂ ; -PS ₂ R⁻; -PS ₂ R ₂ ; -PO ₃ ² ⁻; PO ₃ R⁻; -PO ₃ R ₂ ; -PO ₂ S ² ⁻; -PO ₂ SR⁻; -PO ₂ SR ₂ ; -POS ₂ ² ⁻; -POS ₂ R⁻; POS ₂ R ₂ ; PS ₃ ² ⁻; -PS ₃ R⁻; -PS ₃ R ₂ ; -Oxo; -OR; -S⁻; -SR; -S ₂ ⁻; -S ₂ -R; SO-R; -SO ₃ ⁻; -SO ₃ -R; -SO-NR ₂ ; -SONR ₃ ⁺; -SO ₂ -NR ₂ ; -SO ₂ NR ₃ ⁺; Halogen; -IO; -IR ₂ ; -SCN, -OCN; -NCS; -NCO; -BR ₂ ; -BR ₃ -; -O-BR ₂ , where the alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl and metallocenyl radicals are in turn substituted one or more times with R = R ¹ to R ⁸ and R ¹ to R ^{8 can be} identical or different. 4. transition metal oxoporphine derivatives according to any one of claims 1 to 3, wherein M is selected from the group:
Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Mn, Fe, Ru, Os, Rh, Ir,
especially from the group Ti, Zr, Hf. 5. transition metal porphins according to one of the structural formulas with M from the group Ti, Zr, Hf.
6. Process for the preparation of transition metal oxoporphine derivatives according to one of claims 1 to 5 by reaction of transition metal (+ IV, + III or + II) compounds from the group:
M
M (R ⁹ ) ₄
MY ₃ MY ₂
MO (An⁻) ₂
MO (To ² ⁻)
MO
where M is a transition metal, preferably according to claim 4, R ^{9 is} an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, aryloxy group or heteroaryloxy group, Y is a halogen atom, An⁻ is any monovalent anion and An ² ⁻ is any divalent anion, with suitable isoindolimine analogues and / or dinitriles in high-boiling inert solvents at boiling temperature under protective gas and subsequent hydrolysis. 7. Light filter glasses, characterized net that they are pigments after a metal oxoporphine one of claims 1 to 5 included. 8. Light filter glasses according to claim 7, characterized ge indicates that a metal oxoporphine after one of claims 1 to 5 in a polymeric matrix is distributed. 9. Light filter glasses according to claim 7, characterized ge indicates that the metal oxoporphine by Copolymerization or by dissolving or suspending in a polymer solution with subsequent evaporation of the Lö was introduced into a suitable polymer.   10. Ent laser dyes in substance, solution or solid holding at least one metal oxoporphine according to one of the Claims 1 to 5. 11. Photosensitizers for chemical reactions, in particular in the photochemical generation of carbenes and Singlet oxygen containing at least one metal oxo Porphine derivative according to one of claims 1 to 5. 12. Optical recording medium for recording processes, characterized in that it is a Substrate and there formed at least one metal oxoporphin derivative according to any one of claims 1 to 5 end recording layer. 13. Direct color developer for photographic films and images containing a metal oxoporphine derivative according to one of the An sayings 1 to 5. 14. Photographic films and images containing a metal oxoporphine derivative according to one of claims 1 to 5 as di rect color developer, which is on a suitable support applied and coated with a layer that one contains a suitable washable sensitizer. 15. Homogeneous or heterogeneous catalysts for catalytic, especially photocatalytic oxidations and reduction NEN, containing a metal oxoporphine derivative according to one of the Claims 1 to 5. 16. Solar cells containing a metal oxoporphine derivative one of claims 1 to 5. 17. Solar cells according to claim 16, characterized ge features that semiconducting, the metal oxo layers containing porphine derivative are provided.   18. Membrane for ion-selective electrodes and optodes, because characterized in that metal oxo porphine derivatives according to one of claims 1 to 5 as se selective ion carriers are provided. 19. Use of metal oxoporphine derivatives according to one of the Claims 1 to 5 as signal shift reagents in the nuclear magnetic resonance spectroscopy to determine the structure measurement or quantitative or qualitative analysis of Substances or mixtures of substances. 20. A liquid crystal display device comprising a metal oxo Porphine derivative according to one of claims 1 to 5.