WO2008119797A1 - Dinaphthoquaterrylene as a photosensitizer in solar cells - Google Patents

Abstract

Disclosed are dinaphthoquaterrylene derivatives of general formula (I), wherein the variables have the following meaning: X: both represent COOM or are combined into a radical of formula (x1), (x2), or (x3); Y: one of the two radicals represents a radical of formula (y1) or (y2) and the other radical represents hydrogen; or the two radicals are combined into a radical of formula (y3) or (y4), forming a six-membered ring; or both represent hydrogen.

Description

 Dinaphthoquaterrylene as photosensitizers in solar cells

description

The present invention relates to dinaphthoquaterrylene derivatives of general formula I.

in which the variables have the following meaning:

X together to form a six-membered ring connected to a radical of formula (x1), (x2) or (x3)

(x1) (x2) (x3)

or both a remainder -COOM;

Y one of the two radicals is a radical of the formula (y1)

- L-NR ¹ R ² (yi)

or a radical of the formula (y2)

- L - Z - R (y2) and the other group is hydrogen; with each other to form a six-ring connected to a rest of

Formulas (y3) or (y4)

(y3) (y4)

or both hydrogen;

identical or different radicals: amino -NR ¹ R ² , aryloxy, arylthio, hetaryloxy or hetarylthio, to which in each case further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton of which is represented by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, the entire ring system may be mono- or polysubstituted by the radicals (i), ( ii), (iii), (iv) and / or (v) may be substituted:

(i) CrC ₃ o-alkyl, whose carbon chain is represented by one or more moieties -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -C≡C-, -CR ⁴ = CR ⁴ - , -CO-, -SO- and / or -SO ₂ - may be interrupted and may be mono- or polysubstituted by: C _r C ₂ alkoxy, C _r C ₆ alkylthio, -C≡CR ^4, - CR ⁴ = CR ⁴ ₂ , hydroxy, mercapto, halo, cyano, nitro, -NR ⁹ R ¹⁰ , -NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , -

SO ₃ R ⁷ , -PR ⁷ ₂ , -POR ⁷ R ⁷ , (Het) aryl and / or saturated or unsaturated C ₄ -C ₇ -cycloalkyl, whose carbon skeleton is represented by one or more groups -O-, -S-, - NR ⁴ -, -N = CR ⁴ -, CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, wherein the (het) aryl and cycloalkyl radicals in each case one or may be substituted by Ci-Ci ₈ alkyl and / or the above mentioned substituents for alkyl;

(ii) C ₃ -C ₈ -cycloalkyl whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted and to the further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, the entire ring system may be mono- or polysubstituted by Ci-Ci ₈ alkyl, d-C ₂ alkoxy, -C ₆ - alkylthio, -C≡CR ^4, -CR ⁴ = CR ⁴ _2, hydroxy, mercapto, halogen, cyano, nitro, - NR ⁹ R ^10, - NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , -SO ₃ R ⁷ , -PR ⁷ ₂ and / or -

POR ⁷ R ⁷ ; (Iii) aryl or hetaryl to which further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more moieties -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, may be annelated, wherein the entire ring system may be mono- or polysubstituted by: Ci-Ci ₈ alkyl, ci C ₂ alkoxy, Cr

Ce-alkylthio, -C≡CR ⁴ , -CR ⁴ = CR ⁴ ₂ , hydroxy, mercapto, halogen, cyano, nitro, - NR ⁹ R ¹⁰ , -NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , -SO ₃ R ⁷ , -PR ⁷ ₂ , -POR ⁷ R ⁷ , (Het) aryl, (Het) aryloxy and / or (Het) arylthio, wherein the (het) aryl radicals in each case one or more than once by C ₁ -C ₈ -alkyl, C ₁ -C ₂ -alkoxy, C ₁ -C ₆ -alkylthio, hydroxyl, mercapto, halogen, cyano, nitro, -NR ⁹ R ¹⁰ , -NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ ,

-COOR ⁷ , -SO ₃ R ⁷ , -PR ⁷ ₂ and / or -POR ⁷ R ⁷ may be substituted; (iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals mentioned as substituents for the aryl radicals (iii), where U is a grouping -O-, -S-, -NR ³ -, -CO-, -SO- or -SO ₂ - means; (v) Ci-C ₂ alkoxy, C _r C ₆ alkylthio, -C≡CR ^4, -CR ⁴ = CR ⁴ _2, hydroxy, mercapto,

Halogen, cyano, nitro, -NR ⁹ R ^10, -NR ⁵ COR ^6, -CONR ⁵ R ^6, -SO ₂ NR ⁵ R ^6, -COOR ^7, - SO ₃ R ^7, -PR ⁷ ₂ and / or - POR ⁷ R ⁷ ;

RA is hydrogen, Ci-CI8-alkyl, C _r C ₂ alkoxy, amino, -NR ¹ R ^2, phenoxy, where in each case two vicinal radicals RA to a further saturated or unsaturated

5- to 7-membered ring whose carbon skeleton interrupted by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be connected, wherein the ring system may be mono- or polysubstituted by radicals (i), (ii), (iii), (iv) and / or (v), preferably hydrogen;

B dC ₆ -alkylene, C ₂ -C ₆ -alkenylene, C ₂ -C ₆ -alkynylene, phenylene or combinations of these bridge members which are mono- or polysubstituted by C ₁ -C ₂ -alkyl, nitro, cyano and / or halogen can;

A are identical or different radicals -COOM, -SO ₃ M, -PO ₃ M or -Si (OR) ₃ , in which R is H, CH ₃ and / or C ₂ H ₅ , where n = 1 - 3;

D is phenylene, naphthylene or pyridylene, the _2-alkyl, d-C ₂ alkoxy, hydroxy, nitro and / or halogen may be substituted one or more times by d- Ci;

M is hydrogen, alkali metal cation or [NR ⁵ ₄ ] ⁺ ; L is a chemical bond or an arylene or hetarylene radical of the formulas bonded directly or via ethenylene or ethynylene to the dinaphthoquaterrylene skeleton

- Ar - - Ar - E - Ar -

in which the (het) arylene radicals Ar may be identical or different, may contain heteroatoms as ring atoms and / or have fused saturated or unsaturated 5- to 7-membered rings which may likewise contain heteroatoms, where the entire ring system is a - or multiple times

Phenyl, Ci-C _r C ⁵ R ⁶ may be substituted ₂ alkyl, Ci-C ₂ alkoxy, C ₂ -alkylthio and / or -NR;

E is a chemical bond or a grouping -O-, -S-, -NR ⁴ -, -C≡C-, - CR ⁴ = CR ⁴ - or C _r C ₆ alkylene;

R ¹ , R ² independently of one another are the alkyl radicals (i), cycloalkyl radicals (ii) or (het) aryl radicals (iii) mentioned as substituents for the radicals R; connected to a nitrogen atom-containing, saturated or unsaturated, 5- to 7-membered ring, the carbon chain may be interrupted by one or more groups -O-, -S- and / or -NR ⁴ -, to the one or it is possible for two unsaturated or saturated 4- to 8-membered rings to be fused, the carbon chain of which may also be interrupted by these groups and / or -N =, where the entire ring system may be monosubstituted or polysubstituted by: C 1 -C ₂₄ -alkyl which may be substituted by C 1 -C ₈ -alkoxy, C 1 -C ₈ -alkylthio and / or -NR ⁵ R ⁶ , (Het) aryl which is mono- or polysubstituted by C 1 -C ₈ -alkyl and / or the above radicals specified as substituents for alkyl may be substituted, Ci-Ci ₈ alkoxy, CRCI ₈ alkylthio and / or -NR ⁵ R ^6;

Z is -O- or -S-;

R ^{3 is} one of the substituents for the radicals R mentioned alkyl radicals (i) or (Het) aryl radicals (iii);

R 'is hydrogen;

C 1 -C ₃₀ -alkyl, whose carbon chain is represented by one or more groups - O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -C≡C-, -CR ⁴ = CR ⁴ -, - CO-, -SO- and / or -SO ₂ - may be interrupted and substituted one or more times by the substituents mentioned for the radicals R radicals (ii), (iii), (iv) and / or (v) can be; C ₃ -C ₈ -cycloalkyl, to which further saturated or unsaturated 5- to 7-membered

Rings whose carbon skeleton is represented by one or more groupings -O-, - S-, -NR ⁴ -, -N = CR ⁴ -, -CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be fused, wherein the entire ring system a - or may be substituted several times by the radicals (i), (ii), (iii), (iv) and / or (v) mentioned as substituents for the radicals R; Aryl or hetaryl, to the other saturated or unsaturated 5- to 7-membered

Rings whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, be anneliert, wherein the entire ring system may be mono- or polysubstituted by the substituents for the radicals R radicals mentioned radicals (i), (ii), (iii), (iv), (v ) and / or aryl and / or hetarylazo, which may be substituted in each case by C ₁ -C 10 -alkyl, C ₁ -C ₆ -alkoxy and / or cyano;

R ^{4 is} hydrogen or C 1 -C ₈ -alkyl, where the radicals R ^{4 may be} identical or different if they occur more than once;

R ⁵ , R ⁶ independently of one another: hydrogen; C 1 -C ₈ -alkyl whose carbon chain may be interrupted by one or more groups - O-, -S-, -CO-, -SO- and / or -SO ₂ - and which is mono- or polysubstituted by d-Ci _2- alkoxy, C 1 -C 6 -alkylthio, hydroxy, mercapto, halogen,

Cyano, nitro and / or -COOR ⁸ may be substituted;

Aryl or hetaryl, to each of which further saturated or unsaturated 5- to 7-membered rings, whose carbon skeleton may be interrupted by one or more groups -O-, -S-, -CO- and / or -SO ₂ - be annelated can, wherein the entire ring system may be mono- or polysubstituted by d-Ci ₂ alkyl and / or the above, as substituents for alkyl radicals may be substituted, wherein the radicals R ^{5 may be the} same or different, if they occur several times ;

R ⁷ C-Ci-Ci ₈ -alkyl, the carbon chain by one or more groups - O-, -S-, -CO-, -SO- and / or -SO ₂ - may be interrupted and the one or more times by C ₁ -C ₂ -alkoxy, C ₁ -C ₆ -alkylthio, hydroxy, mercapto, halogen, cyano, nitro and / or -COOR ⁸ may be substituted; Aryl or hetaryl, to each of which further saturated or unsaturated 5- to 7-membered rings, whose carbon skeleton may be interrupted by one or more groups -O-, -S-, -CO- and / or -SO ₂ - be annelated in which the entire ring system may be monosubstituted or polysubstituted by C 1 -C ₂ -alkyl and / or the abovementioned radicals mentioned as substituents for alkyl, where R ^{7 may be the} same or different if they occur several times;

R ⁸ is d-C 18 -alkyl;

R ⁹ , R ¹⁰ CrC ₃₀ -AlkVl, whose carbon chain by one or more groups - O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -C≡C-, -CR ⁴ = CR ⁴ - , -CO-, -SO- and / or -SO ₂ - may be interrupted and may be mono- or polysubstituted by: d- Ci ₂ -Akoxy, d-Ce-alkylthio, -C≡CR ⁴ , -CR ⁴ = CR ⁴ ₂ , hydroxy, -NR ⁵ R ⁶ , -NR ⁵ COR ⁶ , (Het) aryl and / or saturated or unsaturated C ₄ -C ₇ -cycloalkyl, whose

Carbon skeleton can be interrupted by one or more moieties -O-, -S-, -NR ⁴ -, - N = CR ⁴ - and / or -CR ⁴ = CR ⁴ -, wherein the (het) aryl and cycloalkyl radicals each a - or may be substituted by Ci-Ci ₈ -alkyl and / or the above mentioned as substituents for alkyl radicals;

Aryl or hetaryl, to the further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, wherein the entire ring system may be monosubstituted or polysubstituted by: Ci-Ci ₈ alkyl, Ci-Ci _2- alkoxy, C ₁ -C ₆ -alkylthio, -

C≡CR ⁴ , -CR ⁴ = CR ⁴ ₂ , hydroxy, -NR ⁵ R ⁶ , -NR ⁵ COR ⁶ , (Het) aryl, (Het) aryloxy and / or (Het) arylthio, wherein the (Het) aryl radicals may each be mono- or polysubstituted by d-C ₈ alkyl, C _r C ₂ alkoxy, hydroxy, -NR ⁵ R ⁶ and / or -NR ⁵ COR ⁶ may be substituted; with the nitrogen atom bonded to a saturated or unsaturated, 5- to 7-membered ring, the carbon chain of which may be interrupted by one or more -O-, -S- and / or -NR ⁴ - groups, to the one or two unsaturated or unsaturated groups saturated 4- to 8-membered rings may be annealed, the carbon chain may also be interrupted by these groups and / or -N =, wherein the entire ring system may be mono- or polysubstituted by: dC ₂₄ alkyl, the C 1 -C ₈ -alkoxy, C 1 -C ₈ -alkylthio and / or -NR ⁵ R ⁶ may be substituted, (Het) aryl, the one or more times by Ci-Ci ₈ alkyl and / or the above, as Substituents for alkyl mentioned radicals may be substituted, Ci-Ci ₈ -alkoxy, Ci-Ci _8- Alkylthio and / or -NR ⁵ R ⁶ ;

and their use as photosensitizers in solar cells.

In addition, the invention relates to novel dye-sensitized solar cells which contain the quaternaryl derivatives I. The direct conversion of solar energy into electrical energy in solar cells is based on the internal photoelectric effect of a semiconductor material, ie the generation of electron-hole pairs by absorption of photons and the separation of the negative and positive charge carriers at a pn junction or a Schottky contact. The photovoltaic voltage thus generated can cause a photocurrent in an external circuit, through which the solar cell gives off its power.

In this case, only those photons can be absorbed by the semiconductor, which have an energy that is greater than its band gap. The size of the semiconductor band gap thus determines the proportion of sunlight that can be converted into electrical energy.

Thin layers or films of metal oxides are known to be inexpensive solid semiconductor materials (n-type semiconductors), but their absorption is usually not within the visible range of the electromagnetic spectrum due to large band gaps. For use in solar cells, the metal oxides must therefore be combined with a photosensitizer, which absorbs in the wavelength range of sunlight, ie at 300 to 2000 nm, and injects electrons in the electronically excited state in the conduction band of the semiconductor. With the help of an additionally used in the cell redox system, which is reduced at the counter electrode, electrons are returned to the sensitizer and this regenerated.

Of particular interest for use in solar cells are the semiconductors zinc oxide, tin dioxide and in particular titanium dioxide, which are used in the form of nanocrystalline porous layers. These layers have a large surface which is coated with the sensitizer, so that a high absorption of the sunlight is achieved.

Dye-sensitized solar cells based on titanium dioxide as a semiconductor material are, for. In US-A-4,927,721, Nature 353, pp. 737-740 (1991) and US-A-5,350,644 and Nature 395, pp. 583-585 (1998) and EP-A-1 176 646 described. These solar cells contain monomolecular films of transition metal complexes, in particular ruthenium complexes which are bonded to the titanium dioxide layer via acid groups, as sensitizers, and in dissolved form iodine / iodide redox systems or amorphous organic p-conductors based on spirobifluorenes.

As sensitizers, metal-free organic dyes were repeatedly proposed, not least for cost reasons. Thus, for this purpose, US Pat. No. 6,359,211 describes cyanine, oxazine, thiazine and acridine dyes which have carboxyl groups bonded via an alkylene radical for attachment to the titanium dioxide semiconductor.

JP-A-10-189065, 2000-243463, 2001-093589, 2000-100484 and 10-334954 describe various perylene skeleton unsubstituted perylene-3,4: 9,10-tetracarboxylic acid derivatives for use in semiconductor solar cells. Specifically they are: perylenetetracarboxylic diimides which carry carboxyalkyl, carboxyaryl, carboxyarylalkyl or carboxyalkylaryl radicals on the imide nitrogen atoms and / or are imidated with p-diaminobenzene derivatives in which the nitrogen atom of the amino group is substituted by two further phenyl radicals in the p-position Part of a heteroaromatic tricyclic system; Perylene-3,4: 9,10-tetracarboxylic monoanhydride monoimides bearing on the imide nitrogen atom the abovementioned radicals or nonfunctionalized alkyl or aryl radicals, or semicondensates of perylene-3,4: 9,10-tetracarboxylic dianhydride with 1, 2-diaminobenzenes or 1, 8-diaminonaphthalenes, which are converted by further reaction with primary amine into the corresponding diimides or double condensates; Condensates of perylene-3,4: 9,10-tetracarboxylic dianhydride with 1, 2-diaminobenzenes, which are functionalized by carboxyl or amino radicals; and perylene-3,4: 9,10-tetracarboxylic diimides which are imidated with aliphatic or aromatic diamines.

New J. Chem. 26, pp. 1155-1160 (2002) describes the sensitization of titanium dioxide with perylene derivatives that are unsubstituted in the perylene framework (bay positions). Specifically mentioned are 9-dialkylaminoperylene-3,4-dicarboxylic acid anhydrides, perylene-3,4-dicarboximides, which are substituted in the 9-position by dialkylamino or carboxymethylamino and at the imide nitrogen atom is a carboxymethyl or a 2,5 -Di (tert-butyl) phenyl radical, and N-dodecylaminoperylene S ^^ JO-tetracarboxylic monoanhydride monoimide. However, the liquid-electrolyte solar cells based on these perylene derivatives showed significantly lower efficiencies than a solar cell sensitized for comparison with a ruthenium complex.

Finally, in Adv. Mater. 17, pp. 813-815 (2005) for solar cells with spirobifluorenes as an amorphous organic p-conductor an indoline dye has been proposed.

The invention has for its object to provide organic colorants, which are characterized by advantageous application properties, in particular strong light absorption and high stability, and result in solar cells with good efficiencies. The problem was solved by Dinaphthoquaterrylenderivate the above-defined general formula I, their use as photosensitizers in solar cells and the photosensitized solar cells themselves.

The Dinaphthoquaterrylenderivate I have special properties due to their extended π system and differ from the known Quaterrylenderiva- z. B. by a hypsochromic shifted absorption and increased fluorescence quantum efficiency. The derivatives with anchor groups can be used as efficient NIR sensitizers in dye solar cells.

Preferred dinaphthoquaterrylene derivatives are those in which all RA in formula I are hydrogen and both X are connected to a radical of the formula (x1) (dicarboxylic anhydride group) or two carboxy radicals are -COOM.

Preferred dinaphthoquaterrylene derivatives are furthermore those in which all RA in formula I are hydrogen and both X are connected to a radical of the formula (x2) (dicarboxylic acid imide group).

The dinaphthoquaterrylene derivatives I are thus asymmetrically structured dinaphthoquaterrylenetetracarboxylic acid and dicarboxylic acid derivatives.

The Dinaphthoquaterrylenderivate I are functionalized at one end of the molecule (3,4-position) acid. The radicals X are connected to form a six-membered ring to form a radical of the formula (x1), (x2) or (x3)

(x1) (x2) (x3)

The Dinaphthoquaterrylenderivate I can be present not only in anhydride form (x1), but also as free acids or as salts (both radicals X is a radical -COOM). Suitable salts are in addition to the ammonium salts (both NH ₄ ⁺ and tetraalkyl / arylammonium [NR ₄ ⁵ ] ⁺ with the same or different radicals R ⁵ , in particular the alkali metal salts.

In the case of the imide radicals (x2), one or more acid groups A are bonded via a bridge member B to the imide nitrogen atom. Suitable bridge members B are C 1 -C 6 -alkylene radicals and phenylene radicals and combinations of these radicals, eg. B. Alkylenphenylen-, Phenylenalkylen- and Alkylenphenylenal- kylenreste. The phenylene radicals may be mono- or polysubstituted by C 1 -C ₂ -alkyl, C 1 -C 6 -alkoxy, hydroxy, nitro, cyano and / or halogen, but are preferably unsubstituted.

The acid groups A are carboxyl, sulfo or phosphonic acid groups, which may also be present as free acid or in salt form.

Examples of (x2) are

(y5) (y6) (y7)

In the case of the condensate radicals (x3) which are formed by condensation of the dicarboxylic acid anhydride with an o-phenylenediamine containing acid groups, 1,8-diaminonaphthalene or 3,4-diaminopyridine, the acid group A, which in turn may be in salt form, is attached to the aromatic ring system D. bound. The ring system D is otherwise preferably unsubstituted, but may also d-Ci ₂ -alkyl, C ₆ -alkoxy, hydroxy, nitro and / or halogen as substituents.

Particularly preferred dinaphthoquaterrylene derivatives I have an anhydride radical (x1) or the corresponding dicarboxylic acid salt in the 3,4-position.

The Dinaphthoquaterrylenderivate I may be unsubstituted at the other end of the molecule (both Y radicals hydrogen) or in peri-position by exactly one amino radical

(yi)

-L-NR ¹ R ² (yi)

or a (Thio) Etherrest (y2)

-L- Z- R (y2)

be substituted (the second radical Y is accordingly hydrogen),

or as imide (y3) or condensate (y4)

(y3) (y4)

present (both radicals Y are here together with formation of a six-membered ring).

In the case of the amino radicals (y1) and the (thio) ether radicals (y2), the amino function or the (thio) ether function is linked to the dinaphthoquaterryl skeleton via a bridge member L.

The bridge member L may be a chemical bond, d. H. the amino group is bonded directly to the dinaphthoquaterrylene skeleton, or a (het) arylene radical of the formulas bonded directly or via ethylene or ethynylene to the dinaphthoquaterrylene skeleton

- Ar - - Ar-E - Ar -

be.

The (het) arylene radicals Ar may contain heteroatoms as ring atoms and / or have anelated saturated or unsaturated 5- to 7-membered rings, which may also contain heteroatoms. In the case of fused ring systems Ar, the bonds to the dinaphthoquaterrylene skeleton and to the functional group can both originate from the same ring or from different rings. The entire ring system may additionally mono- or polysubstituted by phenyl, d-Ci ₂ -alkyl, C ₁ -C ₁₂ - alkoxy, C _r C ₂ -alkylthio and / or -NR ⁵ R ⁶ to be substituted, Ci-Ci ₂ - Alkyl, C ₁ -C ₁₂ - alkoxy and / or -NR ⁵ R ⁶ are preferred as substituents.

If the bridge member L contains two (Het) aryl radicals Ar, these are preferably identical, but they can also be different. The two groups Ar may be bonded to each other directly or via a group -O-, -S-, -NR ⁴ -, -C≡C-, - CR ⁴ = CR ⁴ - or d-Cβ alkylene be linked. The link E preferably denotes a chemical bond or a grouping -O-, -S-, -NR ⁴ - or -C≡C-.

As examples of suitable bridge members L may be mentioned: 1, 4, 1, 3 and 1, 2-phenylene, 1, 4 and 1, 8-naphthylene, 1, 4- and 2,3-pyrrylene, 2,5-, 2,4- and 2, 3-thienylene, 2,5-, 2,4- and 2,3-furanylene, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-pyridinylene , 2,3-, 2,5-, 2,6-, 3,7-, 4,8-, 5,8- and 6,7-quinolinylene, 2,7-, 3,6-, 4,5 , 2,6-, 3,7-, 4,7- and 4,8-isoquinolinylene, 4,4'-, 3,3'- and 2,2'-biphenylene, 3,3'- and 2, 2'-Bithienylene, 1, 4- [2,5-di (tert-butyl)] phenylene, 1, 4- (2,5-dihexyl) phenylene, 1, 4- [2,5-di (tert. octyl)] phenylene, 1,4-2,5-dodecylphenylene, 1,4-2,5-di (2-dodecyl) phenylene, 4,4'-di (2,2 ', 6 , 6'-tetramethyl) phenylene, 4,4'-di (2,2 ', 6,6'-tetraethyl) phenylene, 4,4'-di (2,2', 6,6'-tetraisopropyl) phenylene, 4,4'-di (2,2 ', 6,6'-tetrahexyl) phenylene, 4,4'-di [2,2', 6,6'-tetra (2-hexyl)] phenylene, 4,4 '- Di [2,2', 6,6'-tetra (tert -octyl)] phenylene, 4,4'-di (2,2 ', 6,6'-tetra-dodecyl) phenylene and 4,4 '- Di [2,2', 6,6'-tetra (2-dodecyl)] phenylene and

where R "is hydrogen, methyl, ethyl or phenyl.

Very particularly preferred bridge members L are a chemical bond, 1,4-phenylene and 4,4'-di (2,2 ', 6,6'-tetramethyl) phenylene.

The radicals R ¹ and R ² in the amino radical (y1) independently of one another may be any of the alkyl radicals (i), cycloalkyl radicals (ii) or (het) aryl radicals (iii) mentioned initially in the definition of the variable R. The radicals R ¹ and R ^{2 are} preferably in particular identical phenyl radicals which are C ₁ -C ₈ -alkyl, C ₁ -C ₂ -alkoxy, C ₁ -C ₆ -alkylthio, -NR ⁵ R ⁶ and / or phenoxy and / or phenylthio , which may each be mono- or polysubstituted by Ci-Ci ₈ alkyl, Ci-Ci ₂ alkoxy, C _r C ₆ alkylthio, -NR ⁵ R ⁶ may be substituted as substituents. Preferably, they are in para-position by C ₁ -C ₄ 8- alkyl, especially branched C ₄ -Ci8 alkyl, z. B. tert-octyl, dC-is-alkoxy, for example, methoxy, or di (Ci-Ci ₈ -alkyl) amino, for example dimethylamino, substituted or unsubstituted.

The radicals R ¹ and R ² may also be linked to a saturated or unsaturated, 5- to 7-membered ring containing the nitrogen atom of the amino radical (y1), whose carbon skeleton is represented by one or more -O-, -S- and - / or -NR ⁴ - (R ⁴ : H or Ci-Ci ₈ alkyl, preferably H or C _r C ₆ alkyl) may be interrupted, to which one or two unsaturated or saturated 4- to 8-membered rings be fused can, whose carbon chain can also be interrupted by these groups and / or -N =, wherein the entire ring system may be mono- or polysubstituted by: C 1 -C ₂₄ -alkyl, which by Ci-Ci ₈ -alkoxy, C-Ci _8- alkylthio and / or -NR ⁵ R ⁶ may be substituted, (Het) aryl which is mono- or polysubstituted by Ci-Ci ₈ alkyl and / or the above, as substituents for alkyl genann- Substituted radicals may be substituted, dC-is-alkoxy, Ci-Ci ₈ -Alkylthio and / or -NR ⁵ R ⁶ , wherein C ₄ -C ₈ alkyl, C 1 -C ₈ alkoxy and -NR ⁵ R ⁶ as substituents are preferred.

Examples of preferred unsubstituted cyclic amino radicals are piperidyl, pyrrolidyl, piperazyl, morpholinyl, thiomorpholinyl, pyrryl, dibenzopyrryl (carbazyl), dibenzo-1, 4-oxiranyl (phenoxazinyl), dibenzo-1, 4-thiazinyl (phenothiazinyl) , Dibenzo

1,4-pyrazyl (phenazinyl) and dibenzopiperidyl, where piperidyl, pyrrolidinyl,

Dibenzopyrryl, dibenzo-1, 4-oxiranyl, dibenzo-1, 4-thiazinyl, dibenzo-1, 4-pyrazyl and

Dibenzopiperidyl are particularly preferred and piperidyl and pyrrolidyl are very particularly preferred.

Suitable starting materials for these cyclic amino radicals are the corresponding cyclic amines or their salts. As examples of suitable substituted and unsubstituted amines may be mentioned:

Piperidine, 2- or 3-methylpiperidine, 6-ethylpiperidine, 2,6- or 3,5-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 4-benzylpiperidine, 4-phenylpiperidine, piperidin-4-ol, 2, 2,6,6-tetramethylpiperidin-4-ylamine, decahydroquinoline and decahydroisoquinoline;

Pyrrolidine, 2-methylpyrrolidine, 2,5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, tropanol, pyrrolidin-3-ylamine, (2,6-dimethylphenyl) pyrrolidin-2-ylmethylamine, (2,6-diisopropylphenyl) pyrrolidine 2-ylmethylamine and dodecahydrocarbazole;

Piperazine, diketopiperazine, 1-benzylpiperazine, 1-phenethylpiperazine, 1-cyclohexylpiperazine, 1-phenylpiperazine, 1- (2,4-dimethylphenyl) piperazine, 1- (2-, 3- or 4-methoxyphenyl) -piperazine, 1- (2-, 3- or 4-ethoxyphenyl) piperazine, 1- (2-, 3- or 4-fluorophenyl) piperazine, 1- (2-, 3- or 4-chlorophenyl) piperazine, 1- ( 2-, 3- or 4-bromophenyl) -piperazine, 1-, 2- or 3-pyridin-2-ylpiperazine and 1-benzo [1,3] dioxol-4-ylmethylpiperazine;

Morpholine, 2,6-dimethylmorpholine, 3,3,5,5-tetramethylmorpholine, morpholine-2- or 3-ylmethanol, 3-benzylmorpholine, 3-methyl-2-phenylmorpholine, 2- or 3-phenylmorphon-Nn, 2 - (4-methoxyphenyl) morpholine, 2- (4-trifluoromethylphenyl) morpholine, 2- (4-chlorophenyl) morpholine, 2- (3,5-dichlorophenyl) morpholine, 3-pyridin-3-ylmorpholine, 5-phenyl - morpholin-2-one, 2-morpholin-2-yl-ethylamine and phenoxazine;

Thiomorpholine, 2- or 3-phenylthiomorpholine, 2- or 3- (4-methoxyphenyl) thiomorpholine, 2- or 3- (4-fluorophenyl) thiomorpholine, 2- or 3- (4-trifluoromethylphenyl) thio- morpholine, 2 - or 3- (2-chlorophenyl) thiomorpholine, 4- (2-aminoethyl) thiomorpholine, 3-pyridin-3-ylthiomorpholine, 3-thiomorpholinone and 2-phenylthiomorpholin-3-one and the thiomorpholine oxides and dioxides. Examples of particularly preferred radicals (y1) are:

with the following meaning of the variables:

L 'chemical bond or 1, 4-phenylene; Z 'is -O-, -S-, -NR ^8' - or -CH ₂ -, wherein R ⁸ 'is C _r Ci ₈ alkyl; R ^IV C ₄ -C ₈ -alkyl ₁ CRCI ₈ -alkoxy odor -NR ⁵ R ⁶

Very particularly preferred amino radicals (y1) are the abovementioned diphenylaminophenylene radicals and in particular the diphenylamino radicals.

For the (thio) ether radical (y2), as bridge members L a chemical bond, 1, 4-phenylene and 2,5-thienylene are particularly preferred. Very particularly preferred bridge member L is the chemical bond.

The radical R ³ in the (thio) ether radical (y2) can be one of the alkyl radicals (i) or (het) aryl radicals (iii) mentioned at the beginning in the definition of the variable R.

Preferably, R ^{3 means} :

Ci-C ₃₀ -alkyl, whose carbon chain by one or more -O-, -S- and / or -NR ⁴ - may be interrupted and may be mono- or polysubstituted by d-C ₂ alkoxy, Hydroxy and / or aryl which may be monosubstituted or polysubstituted by C ₁ -C ₈ -alkyl or C ₁ -C ₆ -alkoxy;

Phenyl, which may be mono- or polysubstituted by: C 1 -C ₈ -alkyl, C 1 -C ₂ -alkoxy, C ₁ -C ₆ -alkylthio, -NR ⁵ R ⁶ and / or phenoxy and / or phenylthio, in each case one or more times C ₆ alkylthio and / or -NR ⁵ R ⁶ may be substituted C _r C ₈ alkyl, C _r C ₂ alkoxy, C _r. Examples of particularly preferred radicals (y2) are:

Phenoxy, phenylthio, naphthyloxy or naphthylthio, each of which may be mono- or polysubstituted by C ₄ -C ₈ -alkyl, C 1 -C -alkoxy and / or -NR ⁵ R ⁶ .

In the imide radicals (y3), R 'can, in addition to hydrogen, denote the alkyl radicals (i), cycloalkyl radicals (ii) or (het) aryl radicals (iii) defined at the outset.

Preferably, R 'has the following meaning:

Cβ-Cso-alkyl whose carbon chain may be interrupted by one or more groups -O-, -S- and / or -NR ⁴ - and which may be mono- or polysubstituted by: C 1 -C ₆ -alkoxy, C 1 -C ₆ -alkylthio , -NR ⁹ R ¹⁰ and / or aryl which may mono- or polysubstituted by d-Ci ₈ alkyl or Ci-C ₆ -alkoxy be substituted, C ₆ -C ₃ O-alkyl substituted by at ω-position -NR ⁹ R ^{10 is} substituted, is particularly preferred;

(Het) aryl, in particular phenyl, naphthyl, pyridyl or pyrimidyl, especially phenyl, which may each be mono- or polysubstituted by: C ₁ -C ₈ -alkyl, C ₁ -C ₆ -alkoxy, halogen, cyano, nitro, - NR ⁹ R ¹⁰ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ and / or phenoxy, phenylthio, phenylazo and / or naphthylazo, which are each substituted by C 1 -C 10 -alkyl, C 1 -C ₆ -alkoxy and / or cyano can.

Most preferably, R 'is a phenyl radical which is mono- or polysubstituted by Ci-Ciβ-alkyl or -NR ⁹ R ¹⁰ .

The radicals R ⁵ and R ⁶ have the meaning given above. Preferably, they independently of one another mean:

Hydrogen; C 1 -C ₈ -alkyl which may be mono- or polysubstituted by C 1 -C ₆ -alkoxy, hydroxyl, halogen and / or cyano;

Aryl or hetaryl, which may each be mono- or polysubstituted by dC ₆ alkyl and / or the above, as substituents for alkyl radicals may be substituted.

Particularly suitable substituents are the alkyl radicals and especially the amino groups -NR ⁹ R ¹⁰ .

The meaning of the radicals R ⁹ and R ¹⁰ is also given at the outset. Preferably, they independently of one another mean:

C 1 -C ₃₀ -alkyl whose carbon chain is interrupted by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -C≡C- and / or -CR ⁴ = CR ⁴ - can be and the one or can be mono- or polysubstituted by d-C ₂ alkoxy, CrC ₆ alkylthio, -C≡CR ^4, - CR ⁴ = CR ⁴ _2, hydroxy, -NR ⁵ R ^6, -NR ⁵ COR ⁶ and / or (Het ) Aryl which may be mono- or polysubstituted by Ci-Ci ₈ alkyl and / or the above, as substituents for alkyl radicals may be substituted; Aryl or hetaryl, to the further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ⁴ -, - N = CR ⁴ -, CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, wherein the entire ring system may be mono- or polysubstituted by: C ₁ -C 8 -alkyl, C ₁ -C ₂ -alkoxy, C _{r is} C ₆ alkylthio, -C (CR ⁴ , -CR ⁴ = CR ⁴ ₂ , hydroxy, - NR ⁵ R ⁶ , -NR ⁵ COR ⁶ , (Het) aryl, (Het) aryloxy and / or (het) arylthio where the (het) aryl radicals can each be monosubstituted or polysubstituted by C ₁ -C 18 -alkyl, C 1 -C ₂ -alkoxy, hydroxyl, -NR ⁵ R ⁶ and / or -NR ⁵ COR ^6, or attached to the nitrogen atom a piperidyl, pyrrolidinyl, dibenzopyrryl, dibenzo-1, 4-oxiranyl, dibenzo-1, 4-thiazinyl, dibenzo-1, 4-pyrazyl or Dibenzopiperi- dylringsystem, which may be mono- or polysubstituted by C 1 -C ₂₄ -alkyl which is represented by C 1 -C ₈ -alkoxy, C 1 -C ₈ -alkylthio and / or -NR ⁵ R ⁶ may be substituted.

The amino groups -NR ⁹ R ¹⁰ are preferably di (het) arylamino groups or cyclic amino groups. Particular preference is given to diphenylamino groups in which the phenyl radicals may be unsubstituted or may have the abovementioned substituents, in particular the alkyl radicals, preferably in the p position.

Preferred substitution patterns for the phenyl radicals R 'are ortho, ortho'-disubstitution (eg alkyl radicals with secondary carbon atom in position 1) and para substitution (eg alkyl radicals with tertiary carbon atom in position 1 and at least 5 carbon atoms or Amino groups -NR ⁹ R ¹⁰ ).

Examples of particularly preferred radicals R 'are:

with the following meaning of the variables:

_R IV C ₄ -C ₈ alkyl or C _r C ₈ alkoxy;

R ^v C _ß -Cs-alkyl with secondary carbon atom in 1-position; R VI is C ₄ -C ₈ alkyl having tertiary carbon atom in 1-position or -NR ⁹ R ¹⁰ ; R ¹ 'is C ¹ -C ₈ alkyl; R ³ 'is phenyl when L' is a chemical bond;

C ₄ -C ₈ -alkyl when L 'is 1, 4-phenylene;

L 'chemical bond, 1, 4-phenylene or 2,5-thienylene; Z 'is -O-, -S-, -NR ⁸ - or -CH ₂ - wherein R ⁸ is C _r C ₈ alkyl;

Z is -O- or -S-.

Very particularly preferred radicals R 'are the Diphenylaminophenylenreste.

The condensate radicals (y4) are formed by condensation of the anhydride with optionally substituted aromatic diamines, in particular with o-phenylenediamine or 1, 8-diaminonaphthalene or else 3,4-diaminopyridine.

Dinaphthoquaterrylene derivatives I are preferred in which one of the two radicals Y is a radical (y1) or (y2) and the other radical is hydrogen or both radicals Y are an imide radical (y3), the abovementioned further preferences apply.

Dinaphthoquaterrylene derivatives I are particularly preferred in which one of the two radicals Y is a radical (y1) or (y2) and the other radical is hydrogen. The dinaphthoquaterrylene derivatives I are preferably additionally substituted on the dinaphthoquaterrylene skeleton. A tetrasubstitution in 1, 6, 1 1, 16-position is preferred. Further substitutions are possible at positions 22, 26 (27) or 22, 23, 26, 27 or 21, 22, 23, 24, 25, 26, 27 and 28. It is also a hexa substitution possible. The counting always begins here at the molecular end with the radicals X.

The dinaphthoquaterrylene derivatives I may be in the form of mixtures of products of varying degrees of substitution in which the tetrasubstituted products constitute the major constituent. Since the substituents are usually introduced into the dinaphthoquaterrylene skeleton by nucleophilic substitution of halogenated, in particular brominated, precursors, the dinaphthoquaterrylene derivatives I can still contain traces of halogen which, if desired, can be removed by transition-metal-catalyzed reductive or base-induced dehalogenation.

Suitable substituents are, in particular, the (het) aryloxy and (het) arylthio radicals R defined at the outset. Phenoxy, thiophenoxy, pyridyl oxy, pyrimidylthio, pyridylthio and pyrimidyloxy radicals are particularly suitable. The radicals R can correspond to radicals of the formula (y2).

Preferred radicals R are phenoxy or thiophenoxy radicals which may each be monosubstituted or polysubstituted by identical or different radicals (i), (ii), (iii), (iv) and / or (v):

(i) C 1 -C ₃₀ -alkyl whose carbon chain is substituted by one or more groups -O-, -S-, -NR ⁴ -, -C≡C-, -CR ⁴ = CR ⁴ - and / or -CO- and / or -SO ₂ - may be interrupted and may be mono- or polysubstituted by d-C ₂ alkoxy, hydroxy, halogen, cyano and / or aryl which is monosubstituted or polysubstituted by CRCI ₈ alkyl or CrC ₆ - Alkoxy may be substituted;

(ii) C ₃ -C ₈ -cycloalkyl, whose carbon skeleton may be interrupted by one or more moieties -O-, -S-, -NR ⁴ -, -CR ⁴ = CR ⁴ - and / or -CO-, and the - or may be substituted several times by Ci-Ci ₈ -alkyl, Ci-Ci _2- AIkOXy and / or dC _6- Alkylthio;

(iii) aryl or hetaryl, to which in each case further 5- to 7-membered saturated or unsaturated rings whose carbon skeleton is represented by one or more groupings -O-, -S-, - NR ⁴ -, -N = CR ⁴ -, - CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted Anne, may be moieties, where the entire ring system may be mono- or polysubstituted by Ci-Ci ₈ alkyl , C _r C ₂ alkoxy, -C≡CR ⁴ _2, -CR ⁴ = CR ⁴ _2, hydroxy, halogen, cyano, -NR ⁹ R ^10, -NR ⁵ COR ^6, -CONR ⁵ R ^6, -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , -SO ₃ R ⁷ , (Het) aryl, (Het) aryloxy and / or (het) arylthio, where the (het) aryl radicals may each be mono- or polysubstituted by C 1 -C ₈ -alkyl, C 1 -C ₈ -alkoxy and / or cyano;

(iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals which are mentioned as substituents for the aryl radicals (iii), where U is a grouping -O-, -S-, -NR ⁴ -, -CO-, -SO- or -SO ₂ -;

(v) C _r C ₂ alkoxy, C _r C ₆ alkylthio, -C≡CR ^4, -CR ⁴ = CR ⁴ _2, hydroxy, mercapto, halogen, cyano, nitro, -NR ⁹ R ^10, -NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ or -SO ₃ R ⁷ .

The (thio) phenoxy radicals R can be unsubstituted or simply substituted in ortho, meta or, preferably, para position. They can also be substituted by two, three, four or five times, all substitution patterns being conceivable.

Suitable radicals R are (thio) phenoxy radicals of the formula

In particular, the variables in the above formula have the following meaning:

Z is -O- or -S-, preferably -0-;

R "same or different radicals:

(i) C 1 -C ₈ -alkyl whose carbon chain may be interrupted by one or more groups -O-, -S-, -NR ⁴ - and / or -CO- and which is mono- or polysubstituted by d -Ci ₂ alkoxy, hydroxy and / or halogen may be substituted, wherein at most one of the radicals R "in 1 position may have a tertiary carbon atom, (ii) Cs-Cs-cycloalkyl, which in the 1-position no tertiary carbon con- tains atom, the ₈ alkyl and / or d-C may be ₂ alkoxy substituted one or more times by Ci-Ci, where at most one of the radicals R "in the 1-position may have a tertiary carbon atom;

(Ii) aryl or hetaryl, which may each be mono- or polysubstituted by C 1 -C ₈ -alkyl, C 1 -C ₂ -alkoxy, hydroxy and / or halogen; (iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the substituents mentioned above as substituents for the aryl radicals (iii), where U is a grouping -O-, -S- or -NR ⁴ - ; (v) _d-Ci2 alkoxy, hydroxy, halogen or cyano; R '"are identical or different radicals: hydrogen, one of the radicals (i), (ii), (iii), (iv) and (v), preferably C ₄ -C ₈ -alkyl radicals mentioned for R", which in the 1 -Position contain a tertiary carbon atom or their carbon chain one or more times by -O-, -S- and / or -NR ⁴ - may be interrupted and / or mono- or polysubstituted by d-Ci ₂ alkoxy, C ₁ -C ₁₂ - alkylthio and / or -NR ⁵ R ⁶ may be substituted;

R ^{4 is} hydrogen or C 1 -C ⁶ -alkyl.

Preferably, the (thio) phenoxy R are only substituted in the para position, in particular by C ₄ -C ₈ alkyl, especially branched C ₄ -C ₈ -alkyl such as tert-octyl, d-CI8-alkoxy, such as methoxy, or di (C 1 -C ₈ -alkyl) amino, such as, for example, dimethylamino.

Furthermore, the dinaphthoquaterrylene skeleton of the dinaphthoquaterrylene derivatives I can also be substituted by amino radicals -NR ¹ R ² . These correspond to the radicals (y1) in which L represents a chemical bond.

The dinaphthoquaterrylene derivatives I can be substituted at the same time by (Het) aryloxy or - (Het) arylthio radicals R and cyclic amino groups -NR ¹ R ² or either by radicals R or by radicals -NR ¹ R ² . However, they are preferably substituted by radicals R.

As examples of the radicals R, R 'to R ^vι occurring in the formulas and R ¹ to R ¹⁰ or their substituents may be mentioned in detail:

Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, nonyl, Isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl (the above names isooctyl, isononyl, isodecyl and isotridecyl are trivial and derived from the alcohols obtained by the oxo process) ;

2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3.7 Dioxanonyl, 4,7-dioxoctyl, 4,7-dioxanonyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9- Trioxaundecyl, 3,6,9-trioxadodecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;

2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl, 2-isopropylthioethyl, 2-butylthioethyl, 2- and 3-methylthiopropyl, 2- and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2- and 3-butylthiopropyl, 2- and 4-methylthiobutyl, 2- and 4-ethylthiobutyl, 2- and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl, 4,8-dithianonyl, 3,7-dithiaoctyl, 3,7 Dithianonyl, 2- and 4-butylthiobutyl, 4,8-dithiadecyl, 3,6,9-trithiadecyl, 3,6,9-thiothia-undecyl, 3,6,9-trithiadodecyl, 3,6,9, 12-tetrathiatridecyl and 3,6,9,12-tetrathiatetra-decyl;

2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2- and 3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and 4-monopropylaminobutyl, 2- and 4-dimethylaminobutyl, 6-methyl-3,6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-di-azaoctyl, 3,6-dimethyl-3,6-diazaoctyl, 9-methyl-3,6,9-triazadecyl, 3,6,9- Trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl, 3,6,9-trimethyl-3,6,9-triazaundecyl, 12-methyl-3,6,9,12-tetraazatridecyl and 3, 6,9,12-tetramethyl-3,6,9,12-tetraazatridecyl;

(I-ethylethylidene) aminoethylene, (1-ethylethylidene) aminopropylene, (1-ethylethylidene) aminobutylene, (1-ethylethylidene) aminodecylene and (1-ethylethylidene) aminododecylene;

Propan-2-one-1-yl, butan-3-one-1-yl, butan-3-one-2-yl and 2-ethyl-pentan-3-one-1-yl;

2-Methylsulfoxidoethyl, 2-Ethylsulfoxidoethyl, 2-Propylsulfoxidoethyl, 2-Isopropylsulf- oxidoethyl, 2-Butylsulfoxidoethyl, 2- and 3-Methylsulfoxidopropyl, 2- and 3-Ethylsulf- oxidopropyl, 2- and 3-Propylsulfoxidopropyl, 2- and 3- Butylsulfoxidopropyl, 2- and 4-methylsulfoxidobutyl, 2- and 4-ethylsulfoxidobutyl, 2- and 4-propylsulfoxidobutyl and 4-butylsulfoxidobutyl;

2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl, 2-isopropylsulfonyl-ethyl, 2-butylsulfonylethyl, 2- and 3-methylsulfonylpropyl, 2- and 3-ethylsulfonylpropyl, 2- and 3-propylsulfonylpropyl, 2- and 3-butylsulfonylproypl, 2- and 4-methylsulfonylbutyl, 2- and 4-ethylsulfonylbutyl, 2- and 4-propylsulfonylbutyl and 4-butylsulfonylbutyl;

Carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl, 8-carboxyctyl, 10-carboxydecyl, 12-carboxydodecyl and 14-carboxytetradecyl;

Sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 6-sulfohexyl, 8-sulfooctyl, 10-sulfodecyl, 12-sulfododecyl and 14-sulfotetradecyl; 2-hydroxyethyl, 2- and 3-hydroxypropyl, 1-hydroxyprop-2-yl, 3- and 4-hydroxybutyl, 1-hydroxybut-2-yl and 8-hydroxy-4-oxo-octyl;

2-cyanoethyl, 3-cyanopropyl, 3- and 4-cyanobutyl, 2-methyl-3-ethyl-3-cyanopropyl, 7-cyano-7-ethylheptyl and 4-methyl-7-methyl-7-cyanoheptyl;

2-chloroethyl, 2- and 3-chloropropyl, 2-, 3- and 4-chlorobutyl, 2-bromoethyl, 2- and 3-bromopropyl and 2-, 3- and 4-bromobutyl;

2-nitroethyl, 2- and 3-nitropropyl and 2-, 3- and 4-nitrobutyl;

Methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, neopentoxy. Pentoxy and hexoxy;

Methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio and hexylthio;

Ethynyl, 1- and 2-propynyl, 1-, 2- and 3-butynyl, 1-, 2-, 3- and 4-pentynyl, 1-, 2-, 3-, 4- and 5-hexynyl, 1- , 2-, 3-, 4-, 5-, 6-, 7-, 8- and 9-decynyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and 11-dodecynyl and 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14 -, 15-, 16- and 17-octadecinyl;

Ethenyl, 1- and 2-propenyl, 1-, 2- and 3-butenyl, 1-, 2-, 3- and 4-pentenyl, 1-, 2-, 3-, 4- and 5-hexenyl, 1- , 2-, 3-, 4-, 5-, 6-, 7-, 8- and 9-decenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9, 10 and 11 dodecenyl and 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14-, 15-, 16- and 17-octadecenyl;

Methylamino, ethylamino, propylamino, isopryplamino, butylamino, isobutylamino, pentylamino, hexylamino, dimethylamino, methylethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, dipentylamino, dihexylamino, dicyclopentylamino, dicyclohexylamino, dicycloheptylamino, diphenylamino and dibenzylamino;

Formylamino, acetylamino, propionylamino and benzoylamino;

Carbamoyl, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl, heptylaminocarbonyl, octylaminocarbonyl, nonylaminocarbonyl, decylaminocarbonyl and phenylaminocarbonyl; Aminosulfonyl, N, N-dimethylaminosulfonyl, N, N-diethylaminosulfonyl, N-methyl-N-ethylaminosulfonyl, N-methyl-N-dodecylaminosulfonyl, N-dodecylaminosulfonyl, (N, N-dimethylamino) ethylaminosulfonyl, N, N- (propoxyethyl) dodecylaminosulfonyl, N, N-diphenylaminosulfonyl, N, N- (4-tert-butylphenyl) octadecylaminosulfonyl and N, N-bis (4-chlorophenyl) aminosulfonyl;

Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, hexoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenoxycarbonyl, (4-tert-butylphenoxy) carbonyl and (4-chlorophenoxy) carbonyl;

Methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, isopropoxysulfonyl, butoxysulfonyl, isobutoxysulfonyl. Butoxysulfonyl, hexoxysulfonyl, dodecyloxysulfonyl, octadecyloxysulfonyl, phenoxysulfonyl, 1- and 2-naphthyloxysulfonyl, (4-tert-butylphenoxy) sulfonyl and (4-chlorophenoxy) sulfonyl;

Diphenylphosphino, di (o-tolyl) phosphino and diphenylphosphine oxido;

Chlorine, bromine and iodine;

Phenylazo, 2-naphthylazo, 2-pyridylazo and 2-pyrimidylazo;

Cyclopropyl, cyclobutyl, cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3- and 4-propylcyclohexyl , 3- and 4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and 4- sec.-butylcyclohexyl, 3- and 4-tert-butylcyclohexyl, cycloheptyl, 2-, 3- and 4-methylcycloheptyl, 2 , 3- and 4-ethylcycloheptyl, 3- and 4-propylcycloheptyl, 3- and 4-isopropylpropylcycloheptyl, 3- and 4-butylcycloheptyl, 3- and 4-sec-butylcycloheptyl, 3- and 4-tert-butylcycloheptyl , Cyclooctyl, 2-, 3-, 4- and 5-methylcyclooctyl, 2-, 3-, 4- and 5-ethylcyclooctyl and 3-, 4- and 5-propylcyclooctyl; 3- and 4-hydroxycyclohexyl, 3- and 4-nitrocyclohexyl and 3- and 4-chlorocyclohexyl;

1-, 2- and 3-cyclopentenyl, 1-, 2-, 3- and 4-cyclohexenyl, 1-, 2- and 3-cycloheptenyl and 1-, 2-, 3- and 4-cyclooctenyl;

2-dioxanyl, 1-morpholinyl, 1-thiomorpholinyl, 2- and 3-tetrahydrofuryl, 1-, 2- and 3-pyrrolidinyl, 1-piperazyl, 1-diketopiperazyl and 1-, 2-, 3- and 4-piperidyl;

Phenyl, 2-naphthyl, 2- and 3-pyrryl, 2-, 3- and 4-pyridyl, 2-, 4- and 5-pyrimidyl, 3-, 4- and 5-pyrazolyl, 2-, 4- and 5 -imidazolyl, 2-, 4- and 5-thiazolyl, 3- (1, 2,4-triazyl), 2- (1, 3,5-triazyl), 6-quinaldyl, 3, 5, 6 and 8-quinolinyl, 2-benzoxazolyl, 2-benzothiazolyl, 5-benzothiadiazolyl, 2- and 5-benzimidazolyl and 1- and 5-isoquinolyl; 1-, 2-, 3-, A-, 5-, 6-, and 7-indolyl, 1-, 2-, 3-, A-, 5-, 6-, and 7-isoindolyl, 5- (4-methyliso - indolyl), 5- (4-phenylisoindolyl), 1-, 2-, A-, 6-, 7- and 8- (1, 2,3,4-tetrahydroisoquinolinyl), 3- (5-phenyl) - ( 1, 2,3,4-tetrahydroisoquinolinyl), 5- (3-dodecyl- (1,2,3,4-tetrahydroisoquinolinyl), 1-, 2-, 3-, 4-, 5-, 6-, 7- and 8- (1,2,3,4-tetrahydroquinolinyl) and 2-, 3-, 4-, 5-, 6-, 7- and 8-chromanyl, 2-, 4- and 7-quinolinyl, 2 - (4-phenylquinolinyl) and 2- (5-ethyl-quinolinyl);

2-, 3- and 4-methylphenyl, 2,4-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 3 , 5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 3,5- and 2,6-dipropylphenyl, 2,4,6- Tripropylphenyl, 2-, 3- and A-isopropylphenyl, 2,4-, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4- , 3,5- and 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and A-isobutylphenyl, 2,4-, 3,5- and 2,6-diisobutylphenyl, 2,4, 6-triisobutylphenyl, 2-, 3- and 4-sec-butylphenyl, 2,4-, 3,5- and 2,6-di-sec-butylphenyl and 2,4,6-tri-seα-butylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 3,5- and 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4- , 3,5- and 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl, 2,4-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3 and 4-isopropoxyphenyl, 2,4- and 2,6-diisopropoxyphenyl and 2-, 3- and 4-butoxyphenyl; 2-, 3- and 4-chlorophenyl and 2,4-, 3,5- and 2,6-dichlorophenyl; 2-, 3- and A-hydroxyphenyl and 2,4-, 3,5- and 2,6-dihydroxyphenyl; 2-, 3- and 4-cyanophenyl; 3- and 4-carboxyphenyl; 3- and 4-carboxamidophenyl, 3- and 4-N-methylcarboxamidophenyl and 3- and 4-N-ethylcarboxamidophenyl; 3- and 4-acetylaminophenyl, 3- and A-propionylaminophenyl and 3- and 4-butyluraminophenyl; 3- and 4-N-phenylamino-phenyl, 3- and 4-N- (o-tolyl) aminophenyl, 3- and 4-N- (m-tolyl) aminophenyl and 3- and 4- (p-tolyl) aminophenyl ; 3- and 4- (2-pyridyl) aminophenyl, 3- and 4- (3-pyridyl) aminophenyl, 3- and 4- (4-pyridyl) aminophenyl, 3- and 4- (2-pyrimidyl) aminophenyl and 4- (4-pyrimidyl) aminophenyl;

4-phenylazophenyl, 4- (1-naphthylazo) -phenyl, 4- (2-naphthylazo) -phenyl, 4- (4-naphthyl-azo) -phenyl, 4- (2-pyrylazo) -phenyl, 4- (3-pyridyl-azo) -phenyl , 4- (4-Pyridylazo) phenyl, 4- (2-pyrimidylazo) phenyl, 4- (4-pyrimidylazo) phenyl and 4- (5-pyrimidylazo) phenyl;

Phenoxy, phenylthio, 2-naphthoxy, 2-naphthylthio, 2-, 3- and 4-pyridyloxy, 2-, 3- and 4-pyridylthio, 2-, A- and 5-pyrimidyloxy and 2-, A- and 5- pyrimidylthio.

The preparation of the dinaphthoquaterrylene derivatives Ia and Ib can advantageously be carried out by the processes described below. The auxiliaries used in this case, such as solvents, bases, catalysts, etc., can of course always be used in the form of mixtures, even without explicitly mentioning them.

If desired, the crude products obtained in each case may be subjected to additional purification by column filtration or column chromatography on silica gel with nonpolar organic solvents, such as hexane or pentane, or polar organic solvents, in particular halogenated hydrocarbons, such as methylene chloride and chloroform, or above all with mixtures of nonpolar and polar solvents become.

0. Preparation of peri-halogendinaphthoquaterrylenedicarboximide IIb

The synthesis starts from the dibromoquaterrylenebis (dicarboximide). The synthesis of Dibromtetraphenoxyquaterrylenbis (dicarboximide) is carried out according to the method described in WO 02/076988.

1st stage

This type of benzene gelation is described in Z. Liu, X. Zhang and RC Larock, JACS 127, pp. 15716-15717 (2005). The reaction succeeds particularly well in a mixture of a polar and a nonpolar solvent.

Preferred non-polar solvents are toluene, aromatic hydrocarbons and ethers, particularly preferred is toluene. Preferred polar solvents are tetrahydrofuran, dimethylformamide and acetonitrile, particularly preferably acetonitrile.

The reaction succeeds particularly well in 9: 1 mixture of toluene and acetonitrile.

The dibromoquaterrylenebisdicarboximide is reacted with a 2-trialkylsilylphenyl triflate, preferably 2-trimethylsilylphenylriflate, in the presence of a base and a palladium catalyst.

Suitable bases are KF, NaF, RbF, LiF, NEt3 and CsF, more preferably CsF.

Suitable palladium catalysts are, for example, Pd (PPh ₃ ) ₄ , Pd (o-tolyl ₃ ) 4, Pd ₂ (dba) ₃ , Pd ₂ (PPhS) ₂ Cl ₂ , Pd ₂ (dba) _{3 being} particularly preferred.

The yield is, for example, about 50%.

The dinaphthoquaterrylenebis (dicarboximide) Nd thus prepared is then saponified and decarboxylated to dibenzoquaterrylene (mono) dicarboximide.

Suitable as saponification reaction medium are polar, in particular protic, organic solvents. Particularly suitable are aliphatic alcohols which have 3 to 8 carbon atoms and may be unbranched, but are preferably branched. In addition to n-propanol and n-butanol, in particular isopropanol, sec- and tert-butanol and 2-methyl-2-butanol may be mentioned by way of example.

Of course, mixtures of solvents can be used. In general, 5 to 500 ml, preferably 20 to 100 ml, of solvent per g of Nd are used.

Suitable bases are alkali metal and alkaline earth metal-containing bases, with the alkali metal-containing bases being preferred and the sodium- and potassium-containing bases being particularly preferred. In this case, both inorganic bases, especially the hydroxides, such as

Sodium hydroxide and potassium hydroxide, as well as organic bases, especially the alcoholates, such as sodium methoxide, potassium methoxide, potassium isopropylate and potassium tert-buty-lat, suitable, which are usually used in anhydrous form. Very particular preference is given to potassium hydroxide.

Of course, mixtures of bases may also be used.

As a rule, from 10 to 200 mol, preferably from 30 to 70 mol, of base per mole of Nd are required.

In particular, in the saponification of dinaphthoquaterrylenetetracarboxylic diimides Nd, it has proved to be advantageous to additionally prepare a metal fluoride, in particular an alkali metal fluoride, e.g. Use potassium fluoride, sodium fluoride or lithium fluoride as an aid.

Suitable amounts of auxiliary are generally from 0.1 to 4 mol, in particular from 0.5 to 1, 5 mol per mol of base.

The reaction temperature is generally 50 to 120 ^° C., preferably 60 to 100 ^° C.

Typical reaction times are 0.5 to 24 h, especially 2 to 10 h.

In terms of process technology, it is expedient to proceed as follows:

A mixture of base, optionally auxiliary and solvent is heated with vigorous stirring to the reaction temperature and then the dinaphthoqua- tylenetetracarboxylic diimide Nd to. After the desired reaction time, an acid, for example an inorganic acid such as hydrochloric acid or preferably an organic acid such as acetic acid, is added dropwise until a pH of about 1 to 4 is reached, and the mixture is stirred at the reaction temperature for a further 1 to 4 hours , The precipitated after cooling to room temperature by dilution with water reaction product is filtered off, washed with hot water and dried in vacuo at about 100 ⁰ C. If, instead of the respective anhydride, the corresponding carboxylic acid salt is to be isolated, the procedure is suitably such that the reaction mixture is not acidified after saponification but only cooled to room temperature, the precipitated product is filtered off and washed with a lower aliphatic alcohol, such as isopropanol and dried at about 100 ⁰ C in vacuo.

Dinaphthoquaterrylenetetracarboxylic monoimide monoanhydride and dinaphthoquaterrentetetracarboxylic dianhydride Ib can be isolated and purified by column chromatography on silica gel with toluene or chloroform as eluent, i. separated from each other and from non-saponified educt II.

The yield of the mixture of dinaphthoquaterrylenetetracarboxylic monoimide monoanhydride and dinaphthoquaterrylenetetracarboxylic dianhydride is usually 70 to 90%.

If desired, the reaction can also be directed in the direction of unilateral or bilateral saponification by selecting suitable reaction conditions (respective process variants b)).

Thus, the one-sided saponification by milder reaction conditions, such as lower base amounts, lower reaction temperatures and shorter reaction times favored, while under more severe reaction conditions, such as larger amounts of bases, auxiliary additive, higher reaction temperatures and longer reaction times, the bilateral saponification outweighs.

Dinaphthoquaterrylenetetracarboxylic monoimide monoanhydride Ia and dinaphthoquateretrylenetetracarboxylic dianhydride Ib can generally be obtained in this way in yields of from 30 to 70% (for Ia) or from 50 to 90% (for Ib).

In the preparation of the dinaphthoquaterrylenedicarboximides advantageously obtained in the saponification of Dinaphthoquaterrylenetetracarbonsäurediimids Nd mixture of Tetracarbonsäuremonoimidmonoanhydrid Ia and tetracarboxylic dianhydride Ib, which usually also contains non-saponified Tetracarbonsäurediimid Nd, and a decarboxylation in the presence of a tertiary nitrogen-based compound as a solvent and a Transition metal catalyst subjected. The dicarboxylic acid imides and dinaphthoquaterrylenes formed in this process can easily be separated from one another by column chromatography.

Of course, the Dinaphthoquaterrylendicarbonsäureimide and the di-naphthoquaterrylenes can also be prepared from the respectively isolated Tetracarbonsäuremonoimidmo- noanhydrid or tetracarboxylic dianhydride. As a reaction medium for the decarboxylation tertiary nitrogen-based compounds are suitable whose boiling point is preferably above the reaction temperature. Examples of particularly suitable solvents are N, N-disubstituted aliphatic carboxylic acid amides (in particular N, N-di-C 1 -C ₄ -alkyl-C 1 -C ₄ -carboxamides) and nitrogen-containing heterocycles.

Specific examples which may be mentioned are dimethylformamide, diethylformamide, dimethylacetamide, dimethylbutyramide, N-methylpyrrolidone, 3-methylpyridine, quinoline, isoquinoline and quinaldine, with quinoline being preferred.

Of course, solvent mixtures can also be used.

In general, 5 to 200 ml, in particular 10 to 70 ml, of solvent are used per g of starting material to be decarboxylated.

Suitable catalysts are in particular the transition metals copper and zinc and their compounds, in particular their oxides and their inorganic and organic salts, which are preferably used in anhydrous form.

Examples of preferred catalysts are copper, copper (I) oxide, copper (II) oxide, copper (I) chloride, copper (II) acetate, zinc acetate and zinc propionate, with copper (I) oxide and zinc acetate being particularly preferred.

Of course, you can also use mixtures of the catalysts mentioned.

In general, 0.5 to 2 mol, preferably 0.9 to 1, 2 mol, catalyst per mole of educt to be decarboxylated used.

The reaction temperature is usually 100 to 250 ^° C., preferably 160 to 220 ^° C.

It is recommended to use under inert gas, e.g. Nitrogen or argon to work.

The decarboxylation is usually completed in 0.5 to 24 hours, especially 1 to 5 hours.

In terms of process technology, it is expedient to proceed as follows: A mixture of educt to be decarboxylated, solvent and catalyst is heated to the desired reaction temperature while being stirred under inert gas. After the desired reaction time and cooling to room temperature, the reaction product is precipitated onto an aqueous acid, in particular dilute hydrochloric acid, and the mixture is stirred at 60 ^° C., if desired, for about 1 hour. The reaction product is filtered off, washed with hot water and heated to about ^100.degree C dried.

Dinaphthoquaterrylenedicarboximide and dinaphthoquaterrylene can be isolated and purified by column chromatography on silica gel with toluene as eluent, i. separated from each other and unreacted educt.

The yield for the mixture of dinaphthoquaterrylenedicarboximide and dinaphthoquaterrylene is, starting from the dinaphthoquaterrylenetetracarboxylic diimide II, usually 65 to 85%.

Finally, the dinaphthoquaterrylene (mono) dicarboximide is halogenated to peri-Halogendinaphthoquaterrylendicarbonsäureimid of formula IIb.

In the preparation of the peri-halogenated dinaphthoquaterrylenedicarboximide IIb, the mixture of dinaphthoquaterrylenedicarboximide and dinaphthoquaterrylene obtained in the above-described decarboxylation, which usually also contains non-saponified dinaphthoquaterrylenetetracarboxylic diimide Nd, which in turn can be used in the saponification of the dinaphthoquaterrylenetetracarboxylic diimide Nd resulting mixture of dinaphtho-quaterrylenetetracarbonsäuremonoimidmonoanhydrid and dinaphthoquaterrylenetetracarboxylic dianhydride based. The resulting halogenated Dinaphthoquaterrylende- derivatives can be easily separated by column chromatography.

Of course, the halogenated Dinaphthoquaterrylenderivate can also be prepared by halogenation of the isolated individual compounds. The halogenation according to the invention is carried out in the presence of a polar organic solvent and a Lewis acid as catalyst with N-halosuccinimide.

This procedure is applicable to produce the chlorinated, brominated or iodinated derivatives, with the chlorinated products being preferred and the brominated products being particularly preferred.

The dinaphthoquaterrylenedicarboximides are mono-halogenated regioselectively in peri-position.

Particularly suitable polar organic solvents for the halogenation are aprotic solvents. Preferred examples of these solvents are the aforementioned aliphatic carboxylic acid amides such as dimethylformamide and dimethylacetamide, and halogenated hydrocarbons such as chloroform and methylene chloride. Particularly preferred is dimethylformamide.

As a rule, 25 to 200 ml, preferably 50 to 150 ml, of solvent per g of starting material to be halogenated are used.

Suitable Lewis acid catalysts are, in particular, metal halides, with iron (III) halides, aluminum trihalides and zinc halides being preferred. Examples which may be mentioned in detail are iron (III) chloride, iron (III) bromide, iron (III) iodide, aluminum trichloride, aluminum tribromide, aluminum triiodide and zinc chloride, the iron halides being particularly preferred.

In general, 0.01 to 0.5 mol, preferably 0.05 to 0.2 mol, of Lewis acid per mole of starting material to be halogenated are used.

The amount of N-halosuccinimide depends on the degree of halogenation desired. Usually, 1 to 6 mol, especially 1 to 4 mol, of N-halosuccinimide are required per halogen atom to be introduced.

The halogenation temperature is generally from 20 to 100 ^° C., preferably from 40 to 80 ^° C.

It is recommended to use under inert gas, e.g. Nitrogen or argon to work.

Typical reaction times are 0.5 to 24 h, especially 1 to 2 h.

In terms of process technology, it is expedient to proceed as follows: A mixture of starting material to be halogenated, Lewis acid, N-halosuccinimide and solvent is heated to the desired reaction temperature while being stirred under protective gas. After completion of the halogenation and cooling to room temperature, the reaction product is precipitated with dilute inorganic acid, for example with dilute hydrochloric acid. The reaction product is filtered off, washed with hot water and dried in vacuo at about 100 ⁰ C.

The halogenated dinaphthoquaterrylenedicarboximide and dinaphthoquaterrylene can be isolated and purified by column chromatography on silica gel with toluene as the eluent, i. separated from each other and from unreacted educt.

A. Preparation of Dinaphthoquaterrylene Derivatives Ia

For the preparation of the dinaphthoquaterrylene derivatives Ia in which a radical Y is an amino radical (y1) or a (thio) ether radical (y2) and the other radical Y is hydrogen, peri-haloquinolacto-quaterrylenedicarboxylic anhydrides of the formula IIa

or peri-Halogendinaphthoquaterrylendicarbonsäureimide of formula IIb

in the R ^{a is} one of the initially mentioned as substituents for the radicals R alkyl radicals (i) or cycloalkyl radicals (ii) and HaI iodine, preferably chlorine and particularly preferably bromine, with the respective radical (y1) or (y2) containing educts ( III).

The reaction conditions depend on the bridge member L contained in each of the radicals (y1) and (y2) and are described separately below.

If peri-halogendinaphthoquaterrylenedicarboximides IIb are used for the reaction with the starting material (III), which may facilitate the reaction because of their better solubility, the peri-substituted dinaphthoquaterrylenedicarboximides of the formula IIb 'obtained in each case must have

be saponified to the dinaphthoquaterrylenedicarboxylic anhydride Ia.

The alkaline saponification can be carried out for all dinaphthoquaterrylenedicarboximides IIb 'under comparable conditions in polar organic solvents.

In particular, protic polar organic solvents are suitable as the reaction medium. Particularly suitable are aliphatic alcohols which have 3 to 8 carbon atoms and may be unbranched, but are preferably branched. In addition to n-propanol and n-butanol, in particular isopropanol, sec. And tert-butanol and 2-methyl-2-butanol may be mentioned by way of example.

Generally, 5 to 500 ml, preferably 20 to 100 ml, of solvent per g of IIb 'are used.

Suitable bases are alkali metal and alkaline earth metal-containing bases, with the alkali metal-containing bases being preferred and the sodium- and potassium-containing bases being particularly preferred are preferred. Both inorganic bases, in particular the hydroxides, such as sodium hydroxide and potassium hydroxide, and organic bases, especially the alcoholates, such as sodium methylate, potassium methoxide, potassium isopropylate and potassium tert-butylate, are suitable, which are usually anhydrous Form are used. Very particular preference is given to potassium hydroxide.

As a rule, 10 to 200 mol, preferably 30 to 70 mol, of base per mol of IIb 'are required.

It has been found to be advantageous to additionally provide a metal fluoride, in particular an alkali metal fluoride, e.g. Use potassium fluoride, sodium fluoride or lithium fluoride as an aid.

Suitable quantities of auxiliaries are generally from 0.1 to 2 mol, in particular from 0.7 to 1.3 mol, per mole of base.

The reaction temperature is generally 50 to 120 ^° C., preferably 60 to 100 ^° C.

Typical reaction times are 0.5 to 24 h, especially 2 to 10 h.

In terms of process technology, it is expedient to proceed as follows:

A mixture of base, optionally auxiliary and solvent are heated to the reaction temperature with vigorous stirring and then the dinaphthoquatrendylenedicarboximide IIb 'is added. After the desired reaction time is allowed to cool to 70-75 ⁰ C. Dannach is dripped so long an acid, z. For example, an inorganic acid such as hydrochloric acid or preferably an organic acid such as acetic acid, until a pH of about 1 to 4 is reached, and stirred for a further 1 to 4 hours at the reaction temperature. The precipitated after cooling to room temperature by dilution with water reaction product is filtered off, washed with hot water and dried in vacuo at about 100 ⁰ C.

If, instead of the respective anhydride, the corresponding carboxylic acid salt is to be isolated, the procedure is suitably such that the reaction mixture is not acidified after saponification but only cooled to room temperature, the precipitated product is filtered off and washed with a lower aliphatic alcohol, such as isopropanol and dried at about 100 ⁰ C in vacuo.

A.1. Preparation of dinaphthoquaterrylene derivatives of the formula Ia1

The preparation of the dinaphthoquaterrylene derivatives Ia1 is described below in sections as a function of the respective bridge member L.

A.1.1. Preparation of dinaphthoquaterrylene derivatives of the formula Ia1 1 (L = chemical bond)

1

To prepare the Dinaphthoquaterrylenderivate Ia1 1 can be a) the peri-Halogendinaphthoquaterrylendicarbonsäureanhydrid IIa or b) the peri-halo dinaphthoquaterrylendicarbonsäureimid IIb in the presence of an aprotic organic solvent and optionally a base or a combination of a transition metal catalyst and a base with an amine of formula IIIa

H-NR ¹ R ² IMa

implement in case b) the saponification described above is to be connected.

If the reaction is carried out in the presence of the transition metal catalyst, it is generally possible to work with lower reaction temperatures and with smaller amounts of amine starting material purple.

In principle, all aprotic solvents which are stable under the reaction conditions and have a boiling point above the selected re suitable reaction temperature, in which the Dinaphthoquaterrylenedukte IIa or IIb and the amine mauve completely and the optionally used catalysts and bases at least partially dissolve, so that substantially homogeneous reaction conditions are present. It is possible to use both polar and nonpolar aprotic solvents, with polar solvents being particularly preferred when no transition metal catalyst is used. If the amine used is purple at the reaction temperature, it can also serve as the reaction medium itself, and the use of a solvent can be omitted.

Examples of suitable polar aprotic solvents are, in particular, N, N-disubstituted aliphatic carboxylic acid amides (in particular N, N-di-C 1 -C ₄ -alkyl-dC ₄ -carbonic acid amides), nitrogen-containing heterocycles without NH functions, dimethyl sulfoxide and aprotic ethers (in particular cyclic ethers, diaryl ethers and di-C ₁ -C ₆ -alkyl ethers of monomeric and oligomeric C ₂ -C ₃ -alkylene glycols which may contain up to 6 alkylene oxide units, especially diethylene glycol di-C ₁ -C ₄ -alkyl ether).

Specific examples of particularly suitable solvents are: N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide and N, N-dimethylbutyramide; N-methyl-2-pyrrolidone, quinoline, isoquinoline, quinaldine, pyrimidine, N-methylpiperidine and pyridine; dimethyl sulfoxide; Tetrahydrofuran, di- and tetramethyltetrahydrofuran, dioxane, diphenyl ether, diethylene glycol dimethyl, diethyl, dipropyl, diisopropyl, di-n-butyl, di-sec-butyl and di- tert-butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl and diethyl ether and triethylene glycol methyl ethyl ether, with dimethylformamide and tetrahydrofuran being preferred.

Examples of suitable nonpolar aprotic solvents are at> 100 ⁰ C boiling solvents from the following groups: aliphatics (in particular Cs-C-is-alkanes), unsubstituted, alkyl-substituted cycloaliphatic and fused (especially unsubstituted C ₇ -C ₀ cycloalkanes C ₆ -C ₈ -cycloalkanes which are substituted by one to three dC ₆ -alkyl groups, polycyclic saturated hydrocarbons having 10 to 18 C-atoms), alkyl- and cycloalkyl-substituted aromatics (in particular benzene, which is substituted by one to three C ₁ -C ₆ Alkyl groups or a C ₅ -C ₈ cycloalkyl radical) and fused aromatics which may be alkyl-substituted and / or partially hydrogenated (in particular naphthalene which is substituted by one to four C 1 -C ₆ -alkyl groups) and mixtures of these solvents.

Specific examples of particularly preferred solvents include: octane, isooctane, nonane, isononane, decane, isodecane, undecane, dodecane, hexadecane and octadecane; Cycloheptane, cyclooctane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, propylcyclohexane, isopropylcyclohexane, dipropylcyclohexane, butylcyclohexane, tert-butylcyclohexane, methylcyclohexane cycloheptane and methylcyclooctane; Toluene, o-, m- and p-xylene, 1, 3,5-trimethylbenzene (mesitylene), 1, 2,4- and 1,2,3-trimethylbenzene, ethylbenzene, propylbenzene, isopropylbenzene, butylbenzene, isobutylbenzene, tert-butylbenzene and cyclohexylbenzene; Naphthalene, decahydronaphthalene (decalin), 1- and 2-methylnaphthalene, and 1- and 2-ethylnaphthalene; Combinations of the aforementioned solvents, as they can be obtained from the high-boiling, partially or fully hydrogenated fractions of thermal and catalytic cracking processes in crude oil or naphtha, for example mixtures of Exxsol ^® type and alkylbenzene ^® Solvesso® type.

Very particularly preferred solvents are xylene (all isomers), mesitylene and especially toluene.

In general, 10 to 1000 ml, preferably 10 to 500 ml, of solvent per g Dinaphthoquaterrylenedukt IIa or IIb used.

Suitable bases are alkali metal and alkaline earth metal-containing bases, the alkali metal-containing bases being preferred and the sodium- and potassium-containing bases being particularly preferred. In this case, both inorganic bases, especially the hydroxides, such as sodium hydroxide and potassium hydroxide, and the salts of weak inorganic acids, especially the carbonates and bicarbonates, and organic bases, especially the alcoholates, such as sodium methoxide, sodium tert-butoxide, Potassium methylate, potassium isopropylate and potassium tert-butoxide, and the salts of weak organic acids, especially the acetates, suitable, which are usually used in anhydrous form.

When carrying out the reaction in the presence of a transition metal catalyst, strong bases, in particular the alcoholates, such as sodium and potassium tert-butoxide, are preferred, while in the absence of the catalyst weak non-nucleophilic bases, especially the salts of weak acids, preferably the carbonates, such as Sodium carbonate, are particularly suitable.

In general, 0.1 to 10 mol, preferably 0.5 to 3 mol, of base per mole of Dinaphthoquaterrylenedukt IIa or IIb are used.

Particularly suitable as the transition metal catalyst are palladium complexes which can be used in combination with free ligand molecules, such as tetrakis (triphenylphosphine) palladium (O), tetrakis (tris-o-tolylphosphine) palladium (0), [1, 2-bis (di - phenylphosphino) ethane] palladium (II) chloride, [1, 1 '- bis (diphenylphosphino) ferrocene] - palladium (II) chloride, bis (triethylphosphine) palladium (II) chloride, bis (tricyclohexylphosphine) palladium (II) acetate, (2,2'-bipyridyl) palladium (II) chloride, bis (triphenylphosphine) -palladium (II) chloride, tris (dibenzylideneacetone) dipalladium (0), 1, 5-cyclooctadiene-palladium (II) chloride, bis ( acetonitrile) palladium (II) chloride and bis (benzonitrile) palladium (II) - chloride, with [1, 1 '- bis (diphenylphosphino) ferrocene] palladium (II) chloride, tetrakis (tri- phenylphosphine) palladium (O) and tris (dibenzylidenacetoπ) dipalladium (0) are preferred.

Usually, the transition metal catalyst in an amount of 1 to 20 mol%, especially 2 to 10 mol%, based on IIa or IIb used.

In general, the simultaneous presence of free ligand molecules, z. B. of tri (tert-butyl) phosphine, triphenylphosphine and tris (o-tolyl) phosphine and 1, 1 '- (2,2'-diphenylphosphino) binaphthalene (BINAP). Usual amounts are 80 to 500 mol%, preferably 100 to 300 mol%, based on the transition metal catalyst.

The molar ratio of amine derivative IIIa to dinaphthoquaterrylene reactant IIa or IIb in the presence of a transition metal catalyst is generally from 5: 1 to 1: 1, in particular 3: 1 to 2: 1, and in its absence usually from 200: 1 to 1: 1, before 50: 1 to 20: 1 in each case. If the amine derivative purple acts as a reaction medium at the same time, this quantitative restriction is omitted.

The reaction temperature is usually in the presence of the catalyst at 25 to 100 ⁰ C, preferably at 70 to 90 ⁰ C, and in its absence at 25 to 200 ⁰ C, preferably at 70 to 170 ⁰ C.

In particular, when using the transition metal catalyst, it is recommended to carry out the reaction under protective gas.

In the presence of the catalyst, the reaction times are usually from 1 to 48 h, in particular from 10 to 20 h, and in the absence of the catalyst usually from 0.5 to 24 h, especially from 1 to 3 h.

A.1.2. Preparation of Dinaphthoquaterrylene Derivatives of the Formula Ia12 (L = -Ar- or -Ar-E-Ar-)

ia12

The phenylene ring Ar represents the placeholder for the (het) arylene radicals -Ar- and -Ar-E-Ar-.

For the preparation of the dinaphthoquaterrylene derivatives Ia12 can be a) the peri-halo-dicarboxylic anhydride IIa or b) the peri-Halogendinaphthoquaterrylen- dicarboximide IIb in the presence of an organic solvent, if desired in admixture with water, and a transition metal catalyst and a base of a Suzuki coupling reaction with a Dioxaborolanyl-substituted amine of formula INb

in which the radicals R ¹¹ are identical or different and are independently hydrogen, dC ₃ -alkyl, C ₅ -C ₈ -cycloalkyl or (het) aryl, which radicals in each case located on a boron atom and R ¹¹ to form a the both oxygen atoms and the boron atom-containing five- or six-membered ring, which may be substituted on the carbon atoms by up to 4 Ci-C ₃₀ alkyl, C ₅ -C ₈ cycloalkyl or (Het) aryl groups may be joined together .

implement in case b) the saponification described above is to be connected.

The dioxaborolanyl-substituted amines INb used as amine-ring are obtained by reacting the corresponding brominated amines INc

with diboranes of formula IV

in the presence of an aprotic organic solvent, a transition metal catalyst and a base.

However, it is also possible to react the peri-halo-di-naphthoquaterrylenedicarboximide IIb by analogous reaction with the diborane IV into the peri-dioxaborolanyl derivative IIb "

then pass this to the Suzuki coupling with the brominated amine INc.

For the preparation of the dioxaboranyl derivatives INb or IIb ', diboranes IV are, in particular, bis (1,2- and 1,3-diolato) diboranes, tetraalkoxydiboranes, tetracycloalkoxydiboranes and tetra (het) aryloxydiboranes and also their mixed forms. Examples of these compounds are: bis (pinacolato) diborane, bis (1,2-benzenediolato) diborane, bis (2,2-dimethyl-1,3-propanediolato) diborane, bis (1,1,3,3 tetra-methyl-1, 3-propanediolato) diborane, bis (4,5-pinanediolato) diborane, bis (tetramethoxy) diborane, bis (tetra-cyclopentoxy) diborane, bis (tetraphenoxy) diborane and bis (4 - pyridiyloxy) diborane.

Preference is given to diboranes IV in which the two radicals R ¹¹ located on a boron atom are bonded together to form a five-membered or six-membered ring containing the two oxygen atoms and the boron atom. Aromatic or saturated, also bicyclic, rings with 5 to 7 C atoms can be fused to the five- or six-membered rings formed as ring members. All rings or ring systems can be substituted by up to 4 dC ₃ o-alkyl, C ₅ -C ₈ -cycloalkyl, aryl and / or hetaryl radicals, preferably they are substituted by up to 4 dC ₄ -alkyl radicals , Examples of these preferred diboranes are the above-mentioned bis (1, 2 and 1, 3-diolato) -diborane, with bis (pinacolato) diborane being particularly preferred.

The molar ratio of diborane IV to the educt INc or IIb is generally from 0.8: 1 to 3: 1, in particular from 1, 5: 1 to 2: 1.

Suitable solvents are in principle all stable under the reaction conditions against bases aprotic solvent having a boiling point above the selected reaction temperature in which the starting materials at reaction temperature completely and the catalysts and bases used at least partially dissolve, so that substantially homogeneous reaction conditions. It is possible to use both apolar aprotic and polar aprotic solvents, the nonpolar aprotic solvents, in particular toluene, being preferred. Examples of other particularly suitable non-polar and polar aprotic solvents are the solvents listed in Section A.1.1.

The amount of solvent is generally 10 to 1000 ml, preferably 20 to 300 ml, per g INc or IIb.

Suitable transition metal catalysts are, in particular, the palladium complexes mentioned in Section A.1.1, which in turn are generally used in amounts of from 1 to 20 mol%, in particular from 2 to 10 mol%, based on INc or IIb. The additional presence of free ligand molecules is usually not required.

The bases used are preferably the alkali metal salts, in particular the sodium and especially the potassium salts, weak organic and inorganic acids, such as sodium acetate, potassium acetate, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate. Preferred bases are the acetates, especially potassium acetate.

In general, 1 to 5 mol, preferably 2 to 4 mol, of base are used per mole of INc or IIb.

The reaction temperature is usually from 20 to 180 ⁰ C, especially at 60 to 120 ⁰ C.

The reaction time is usually 0.5 to 30 hours, in particular 1 to 20 hours.

In terms of process technology, it is expedient to proceed as follows in the preparation of the dioxaboranyl derivatives:

The starting material INc or IIb and solvent are added, diborane IV, the transition metal catalyst and the base are added in succession and the mixture is heated for 0.5 to 30 h under protective gas to the desired reaction temperature. After cooling to room temperature, the solid components are filtered from the reaction mixture and the solvent is distilled off under reduced pressure.

The Suzuki coupling between the peri-halo-dinaphthoquaterrylenedicarboxylic acid derivative IIa or IIb and the dioxaborolanyl-substituted amine INb or between the dioxaborolanyldinaphthoquaterrylene derivative IIb 'and the p-bromophenylamine INc is carried out in the presence of an organic solvent, if desired in admixture with water, as well as a transition metal catalyst and a base.

The molar ratio of INb to IIa or IIb is generally 0.8: 1 to 3: 1, preferably 0.9: 1 to 2: 1. The molar ratio of IIb 'to INc is generally 0.8: 1 to 3: 1, preferably from 1, 5: 1 to 2.5: 1.

Suitable solvents for the Suzuki coupling are all solvents in which the starting materials are completely dissolved at the reaction temperature and the catalysts and bases used are at least partially dissolved, so that substantially homogeneous reaction conditions are present. Particularly suitable are the solvents mentioned above for the preparation of Dioxaborolanylderivate, wherein also here the alkyl-substituted benzenes are preferred. The amount of solvent is usually from 10 to 1000 ml, preferably from 20 to 100 ml, per g Dinaphthoquaterrylenderivat.

Preferably, water is used as an additional solvent. In this case, 10 to 1000 ml, in particular 250 to 500 ml, of water per I of organic solvent are generally used.

As transition metal catalysts, palladium complexes are again preferably used, the same preferences apply. The amount of catalyst used is usually 1 to 20 mol%, in particular 1, 5 to 5 mol%, based on the Dinaphthoquaterrylenderivat.

As the base, in turn, the alkali metal salts of weak acids are preferred, the carbonates, such as sodium carbonate and especially potassium carbonate, are particularly preferred. In general, the amount of base is from 0.1 to 10 mol, in particular from 0.2 to 5 mol, per mole of dinaphthoquaterrylene derivative.

The reaction temperature is generally from 20 to 180 ^° C., preferably from 60 to 120 ^° C. If water is used in step b), it is advisable not to carry out the reaction at temperatures above 100 ^° C., since otherwise it would be necessary to work under pressure.

The reaction is usually completed in 0.5 to 48 hours, especially in 5 to 20 hours.

In terms of process engineering, the Suzuki coupling is advantageously carried out as follows:

The reactants and solvents are added, transition metal catalyst and the base, which is preferably dissolved in water or a water / alcohol mixture, are added and the mixture is heated for 0.5 to 48 h under inert gas to the desired reaction temperature. After cooling to room temperature, the organic phase is separated from the reaction mixture and the solvent is distilled off under reduced pressure.

A.1.3. Preparation of Dinaphthoquaterrylene Derivatives of the Formula Ia13 (L = Ethylene-linked (het) arylene radical -Ar- or -Ar-E-Ar-)

The phenylene ring Ar again represents the placeholder for the (het) arylene radicals -Ar- and -Ar-E-Ar-.

To prepare the dinaphthoquaterrylene derivatives Ia13, it is possible to use a) the peri-halo-dinaphthoquaterrylenedicarboxylic anhydride IIa or b) the peri-halodinaphthoquaterrylenedicarboximide IIb in the presence of an aprotic organic solvent, a transition metal catalyst, a base and, if desired, a cocatalyst in a Heck reaction with a vinylamine the formula INd

implement in case b) the saponification described above is to be connected.

Particularly suitable solvents for this reaction are polar, but also apolar, aprotic organic solvents. In addition to the solvents listed in Section A.1.1 z. As well as halogenated hydrocarbons and aliphatic amines suitable as a solvent. Specific examples of particularly suitable solvents are: diethylamine, piperidine, tetrahydrofuran, dimethylformamide, N-methylpyrrolidone, methylene chloride, dimethyl sulfoxide and toluene.

Suitable transition metal catalysts are the palladium compounds likewise listed in Section A.1.1, which are also prepared in situ from palladium salts, such as palladium (II) - acetate, and ligand molecules can be made. In general, the direct presence of palladium complexes also recommends the simultaneous presence of free ligand molecules. Examples of particularly preferred transition metal catalyst systems are tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0) and palladium (II) acetate as well as triphenylphosphine and tris (o-tolyl) phosphine.

As cocatalysts alkali metal halides and quaternary ammonium salts can be used. Examples include lithium chloride, tetrabutyl ammonium chloride, bromide and hydrogen sulfate.

Suitable bases are in addition to the alkali metal salts, in particular the sodium and potassium salts, weak inorganic and organic acids and tertiary amines. Examples of particularly suitable bases are sodium bicarbonate, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate and tri (C ₂ -C ₄ -alkyl) amines, such as triethylamine.

The reaction temperatures are usually 0 to 150 ⁰ C, preferably 25 to 80 ⁰ C.

It is recommended to work under inert gas.

The reaction is usually completed in 1 to 24 hours.

Further details on this reaction can be found in Chem. Rev. 100, p. 3009-3066 (2000).

A.1.4. Preparation of Dinaphthoquaterrylene Derivatives of the Formula Ia14 (L = H-linked aryl radical -Ar- or -Ar-E-Ar- via E-thinylene)

The phenylene ring Ar again represents the placeholder for the (het) arylene radicals -Ar- and -Ar-E-Ar-. For the preparation of the dinaphthoquaterrylene derivatives Ia14 can be a) the peri-Halogendinaphthoquaterrylendicarbonsäureanhydrid IIa or b) the peri-halo dinaphthoquaterrylenedicarbonsäureimid IIb in the presence of an aprotic organic solvent, a transition metal catalyst, a base and, if desired, a copper cocatalyst with an ethynylamine of the formula Never

implement in case b) the saponification described above is to be connected.

Particularly suitable solvents for this reaction are polar but also nonpolar organic solvents. In addition to the solvents listed in Section A.1.1 z. As well as halogenated hydrocarbons and amines as solvents suitable. Specific examples of particularly suitable solvents include: diethylamine, piperidine, tetrahydrofuran, dimethylformamide, methylene chloride and toluene.

Suitable transition metal catalysts are the palladium complexes likewise listed in Section A.1.1, with tetrakis (triphenylphosphine) palladium (0) and bis (tri- phenylphosphine) palladium (II) chloride being preferred.

As cocatalysts, copper (I) and copper (II) compounds can be used. In addition to the oxides, copper salts of organic and, in particular, inorganic acids, in particular copper (I) iodide, are also suitable.

Suitable bases are, in addition to the alkali metal salts, in particular the cesium salts, weak inorganic and organic acids, also secondary and tertiary amines. Examples of particularly suitable bases are cesium carbonate, di (C ₂ -C ₄ -alkyl) amines, such as diethylamine and diisopropylamine, tri (C ₂ -C ₄ -alkyl) amines, such as triethylamine, and cyclic amines, such as piperidine.

The reaction temperatures are usually 0 to 150 ⁰ C, preferably 25 to 80 ⁰ C.

It is recommended to work under inert gas.

The reaction is usually completed in 1 to 24 hours. Further details on this reaction can be found in Chem. Rev. 103, pp. 1979-2017 (2003).

A.2. Preparation of dinaphthoquaterrylene derivatives of the formula Ia2

The preparation of the dinaphthoquaterrylene derivatives Ia2 is described below in sections depending on the respective bridge member L.

A.2.1. Preparation of dinaphthoquaterrylene derivatives of the formula Ia21 (L = chemical bond)

To prepare the dinaphthoquaterrylene derivatives Ia21, it is possible to use a) the peri-halo-dinaphthoquaterrylenedicarboxylic anhydride IIa or b) the peri-halo-dinaphthoquaterrylenedicarboximide IIb in the presence of a non-nucleophilic solvent and a base with a (thio) alcohol of the formula Va

H-ZR "Va

implement in case b) the saponification described above is to be connected.

Suitable non-nucleophilic solvents for this reaction are in particular polar aprotic solvents, in particular aliphatic carboxylic acid amides (preferably N, N-di-C 1 -C ₄ -alkyl-C 1 -C ₄ -carboxamides) and lactams, such as dimethylformamide, diethylformamide, dimethylacetamide, dimethylbutyramide and N-methylpyrrolidone.

Non-polar aprotic solvents may also be used as non-nucleophilic solvents, but these solvents are not preferred. By way of example, aromatic hydrocarbons, such as benzene, toluene and xylene, may be mentioned.

The amount of solvent depends on the solubility of the halogenated Dinaphthoquater- rylenderivats. As a rule, from 2 to 200 ml, in particular from 3 to 150 ml of solvent per g of dinaphthoquaterrylene educt IIa or IIb are required.

Suitable bases are, in particular, inorganic and organic alkali or alkaline earth metal-containing bases, the alkali metal-containing bases being particularly suitable. Examples of inorganic bases are alkali metal and alkaline earth metal carbonates and hydrogen carbonates, hydroxides, hydrides and amides; examples of organic bases are alkali metal and alkaline earth metal alcoholates (in particular the C ₁ -C ₄ alkoxides, especially tert-C ₄ -C ₆₎ -Alcoholates), - (phenyl) alkylamides (in particular the bis (C 1 -C ₄ -alkyl) amides) and triphenylmethyl metallates. Preferred bases are the carbonates and hydrogen carbonates, with the carbonates being particularly preferred. Preferred alkali metals are lithium, sodium, potassium and cesium, particularly suitable alkaline earth metals are magnesium and calcium.

Specific examples of the metal-containing bases include: lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; Sodium bicarbonate and potassium bicarbonate; Lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; Lithium hydride, sodium hydride and potassium hydride; Lithium amide, sodium amide and potassium amide; Lithium methylate, sodium methoxide, potassium methoxide, lithium ethylate, sodium ethylate, potassium ethylate, sodium isopropylate, potassium isopropylate, sodium tert-butoxide, potassium tert-butylate, lithium (1,1-dimethyl) octylate, sodium (1, 1). dimethyl) octylate and potassium (1, 1-dimethyl) octylate; Lithium dimethylamide, lithium diethylamide, lithium diisopropylamide, sodium diisopropylamide, lithium hexamethyldisilazide, sodium hexamethyldisilazide, potassium hexamethyldisilazide triphenylmethyllithium, triphenylmethyl sodium and triphenylmethylpotassium.

In addition to these metal-containing bases, purely organic nitrogen-containing bases are also suitable.

Suitable examples thereof are alkylamines, in particular tri (C ₂ -C ₆ -alkyl) amines, such as

Triethylamine, tripropylamine and tributylamine, alcohol amines, in particular mono-, di- and tri (C ₂ -C ₄ -alcohol) amines, such as mono-, di- and triethanolamine, and heterocyclic

Bases such as pyridine, 4- (N, N-dimethylamino) pyridine, (4-pyrrolidino) pyridine, N-methyl piperidine, N-methylpiperidone, N-methylmorpholine, N-methyl-2-pyrrolidone, pyrimidine, quinoline, isoquinoline, quinaldine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) and diazabicycloundecene (DBU).

Very particularly preferred bases are lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate.

As a rule, at least 0.4 equivalents of base are required per mole of (thio) alcohol Va. Particularly suitable amounts used for the metal bases are from 0.4 to 3, in particular from 0.4 to 1.2, equivalents per mole of Va. In the case of purely organic bases, the amount used is preferably from 0.4 to 10, particularly preferably 0, 4 to 3, equivalents per mole of Va. If the organic base is used simultaneously as a solvent, which may be the case in particular in the case of the heterocyclic bases, a quantitative limitation is of course superfluous.

The reaction can be carried out in the presence of phase transfer catalysts.

Particularly suitable phase transfer catalysts are quaternary ammonium salts and phosphonium salts, such as tetra (C 1 -C 18 -alkyl) ammonium halides and tetrafluoroborates, benzyltri (C 1 -C 18 -alkyl) ammonium halides and tetrafluoroborates and tetra (C 1 -C ₈ -alkyl) - and Tetraphenylphosphoniumhalogenide, and crown ethers suitable. The halides are generally the fluorides, chlorides, bromides and iodides, the chlorides and bromides being preferred. More particularly suitable examples are: tetraethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium tetrafluoroborate and benzyltriethylammonium chloride; Tetrabutylphosphonium bromide and tetraphenylphosphonium chloride and bromide; 18-crown-6, 12-crown-4 and 15-crown-5.

If a phase transfer catalyst is used, its amount used is usually 0.4 to 10, in particular 0.4 to 3, equivalents per mole of (thio) alcohol Va. In general, 1 to 10 mol, preferably 1 to 5 mol, (Thio ) Alcohol Va per mole of dinaphthoquaterrylene educt IIa or IIb used.

The reaction temperature depends on the reactivity of the substrate and is generally in the range of 30 to 150 ^° C.

The reaction time is usually 0.5 to 96 hours, especially 2 to 72 hours.

A.2.2. Preparation of dinaphthoquaterrylene derivatives of the formula Ia22 (L = -Ar- or -Ar-E-Ar-)

The phenylene ring Ar represents the placeholder for the (het) arylene radicals -Ar- and -Ar-E-Ar-.

The preparation of the dinaphthoquaterrylene derivatives Ia22 can be carried out analogously to the preparation of the dinaphthoquaterrylene derivatives Ia12 described in Section A.1.2.

Accordingly, a) the peri-halo-dinaphthoquaterrylenedicarboxylic acid anhydride IIa or b) the peri-halo-dinaphthoquaterrylenedicarboximide IIb in the presence of an organic solvent, if desired mixed with water, and a transition metal catalyst and a base of a Suzuki coupling reaction with a dioxaborolanyl-substituted ( Thio) alcohol of the formula Vb

in which the radicals R ^{11 are} identical or different and independently of one another and independently of one another are hydrogen, C ₁ -C 30 -alkyl, C ₅ -C ₈ -cycloalkyl or (Het) aryl, where the radicals R ^{11 present} on one boron atom each also with the formation of a five- or six-membered ring containing the two oxygen atoms and the boron atom, which may be substituted on the carbon atoms by up to 4 C 1 -C ₃₀ -alkyl, C ₅ -C ₈ -cycloalkyl or (het) aryl groups to be connected with each other,

subject in case b) the saponification described above is to be connected.

The dioxaborolanyl-substituted (thio) alcohols Vb used here as an amineuct are analogous to the dioxaborolanyl-substituted amines INc by reaction of the corresponding brominated (thio) alcohols Vc

with diboranes of formula IV

in the presence of an aprotic organic solvent, a transition metal catalyst and a base.

However, here too, the peri-halo-dinaphthoquaterrylenedicarboximide IIb can be converted into the peri-dioxaborolanyl derivative IIb by analogous reaction with the diborane IV "

then convert this to the Suzuki coupling with the brominated (thio) alcohol Vc.

Further details of these reactions can be found in the description of the analogous reactions in Section A.1.2.

A.2.3. Preparation of Dinaphthoquaterrylene Derivatives of the Formula Ia23 (L = ethylene-linked (het) arylene radical -Ar- or -Ar-E-Ar-)

The phenylene ring Ar again represents the placeholder for the (het) arylene radicals -Ar- and -Ar-E-Ar-.

The preparation of the dinaphthoquaterrylene derivatives Ia23 can be carried out analogously to the preparation of the dinaphthoquaterrylene derivatives Ia13 described in section A.1.3.

Accordingly, a) the peri-haloquinolacto-quaterrylene-dicarboxylic anhydride IIa or b) the peri-halo-dinaphthoquaterrylenedicarboximide IIb in the presence of an aprotic organic solvent, a transition metal catalyst, a base and, if desired, a cocatalyst in a Heck reaction with a vinyl (thio) alcohol of the formula vd

implement in case b) the saponification described above is to be connected.

Further details of this implementation can be found in Section A.1.3.

A.2.4. Preparation of Dinaphthoquaterrylene Derivatives Ia24 (L = ethinylene-linked (het) arylene radical -Ar- or -Ar-E-Ar-)

The phenylene ring Ar again represents the placeholder for the (het) arylene radicals - Ar- and -Ar-E-Ar-.

The preparation of the dinaphthoquaterrylene derivatives Ia24 can again be carried out analogously to the preparation of the dinaphthoquaterrylene derivatives Ia14 described in Section A.1.4.

Accordingly, a) the peri-Halogendinaphthoquaterrylendicarbonsäure- anhydride IIa or b) the peri-Halogendinaphthoquaterrylendicarbonsäureimid IIb in the presence of an aprotic organic solvent, a transition metal catalyst, a base and, if desired, a copper cocatalyst with an ethynyl (thio) alcohol of the formula Ve

implement in case b) the saponification described above is to be connected.

Further details of this implementation can be found in Section A.1.4.

A.3. Preparation of dinaphthoquaterrylene derivatives of the formula Ia3

For the preparation of the dinaphthoquaterrylenetetracarboxylic monoimide monoanhydrides Ia3

a Dinaphthoquaterrylentetracarbonsäuredianhydrid of formula Nc

in the presence of a polar aprotic solvent and an imidation catalyst with a primary amine of formula VI

R'-NH ₂ VI

implement.

Particularly suitable polar aprotic solvents are aprotic nitrogen heterocycles, such as pyridine, pyrimidine, imidazole, quinoline, isoquinoline, quinaldine, N-methylpiperidine, N-methylpiperidone and N-methylpyrrolidone, carboxylic acid amides, such as dimethylformamide and dimethylacetamide, and tetraalkylureas, such as tetramethylurea. wherein N-methylpyrrolidone is particularly preferred.

As a rule, 2 to 500 ml, preferably 2 to 50 ml, of solvent per g of Nc are used.

Particularly suitable as imidation catalysts are Lewis acidic salts of organic and inorganic acids with metals, such as zinc, iron, copper and magnesium, and the oxides of these metals, eg. As zinc acetate, zinc propionate, zinc oxide, iron (II) acetate, iron (III) chloride, iron (II) sulfate, copper (II) acetate, copper (II) oxide and magnesium acetate, with zinc acetate is particularly preferred. The salts are preferably used in anhydrous form.

Usually 20 to 500 mol%, in particular 80 to 120 mol% of catalyst, based on Nc, are used.

You can also the acids themselves, so z. As organic acids, in particular C ₁ -C3 carboxylic acids such as formic acid, acetic acid and propionic acid, and inorganic

Acids, such as phosphoric acid, in each case preferably in the most concentrated form, as

Use imidation catalysts. The acids simultaneously serve as solvents medium or as cosolvent and are therefore usually used in excess.

The molar ratio of primary amine VI to dinaphthoquaterrylene-tetracarboxylic dianhydride Nc is usually about 0.1: 1.5 to 0.5: 1.2, especially 0.8: 1.5 to 0.8: 1.2.

The reaction temperature is generally from 60 to 250 ^° C., preferably from 100 to 230 ^° C., particularly preferably from 90 to 170 ^° C.

It is recommended to carry out the reaction under protective gas.

The reaction is usually completed in 1 to 4 hours.

B. Preparation of Dinaphthoquaterrylene Derivatives Ib

In the preparation of the dinaphthoquaterrylene derivatives Ib in which the two radicals X are bonded to an acid group-containing imide radical (x2) or condensate radical (x3), the dinaphthoquaterrylene derivatives Ia can advantageously be used as starting material which have the respective desired radicals Y.

B.1. Preparation of dinaphthoquaterrylene derivatives of the formula Ib1

The preparation of the dinaphthoquaterrylene derivatives Ib1 is described below in sections depending on the substituents Y.

B.1.1. Preparation of dinaphthoquaterrylene derivatives Ib11

The preparation of the dinaphthoquaterrylene derivatives Ib1 1 can be carried out by reacting the corresponding dinaphthoquaterrylene derivatives Ia1

with a primary amine of formula VII

A-B-NH, VII

in the presence of a polar aprotic solvent and an imidation catalyst.

This imidization reaction can be carried out analogously to the imidization reaction described in Section A.3 for the preparation of the dinaphthoquaterrylenetetracarboxylic monoimide monoanhydrides Ia3.

Alternatively, the imidation can also be carried out with larger amounts of primary amine VI (usually 1 to 10 ml, preferably 2 to 6 mol, per mol of Ia1) in the presence of the polar aprotic solvent and an alkali metal or alkaline earth metal-containing base.

Preference is given here to the alkali metal-containing bases, in particular the sodium- and potassium-containing bases. They are both inorganic bases, especially the hydroxides, such as sodium hydroxide and potassium hydroxide, as well as organic bases, especially the Alcohols such as sodium methylate, potassium, potassium isopropoxide and potassium tert-butoxide, suitable, which are usually used in anhydrous form. Very particular preference is given to potassium hydroxide.

In general, 1 to 10 mol, preferably 2 to 4 mol, of base, per mole of Ia1 needed.

The reaction temperature is generally 50 to 200 ^° C., preferably 60 to 150 ^° C.

Typical reaction times are 0.5 to 24 h, especially 2 to 10 h.

B.1.2. Preparation of dinaphthoquaterrylene derivatives of the formula Ib12

The preparation of the Dinaphthoquaterrylenderivate Ib12 can analogously by reaction of the corresponding Dinaphthoquaterrylenderivate Ia2

with a primary amine of formula VII

A-B-NH, VII

in the presence of a polar aprotic solvent and an imidation catalyst. Further details for carrying out this imidization reaction can be found again in Section A.3.

Alternatively, as described in Section B.1.1, the imidation can also be carried out with relatively large amounts of amine VII in the presence of the polar aprotic solvent and of a (meth) alkali metal-containing base.

B.1.3. Preparation of dinaphthoquaterrylene derivatives of the formula Ib13

Also, the Dinaphthoquaterrylenderivate Ib13 are analogous by reaction of the corresponding Dinaphthoquaterrylenderivate Ia3

with a primary amine of formula VII

A-B-NH, VII

in the presence of a polar aprotic solvent and an imidation catalyst.

Further details for carrying out this imidization reaction can be found again in Section A.3. The imidization can also be carried out, as described in Section B.1.1, with relatively large amounts of amine VII in the presence of the polar aprotic solvent and of a (meth) alkali metal-containing base.

B.1.4. Preparation of dinaphthoquaterrylene derivatives of the formula Ib14

As starting material for the preparation of Dinaphthoquaterrylenderivate Ib14

the corresponding dinaphthoquaterrylene derivatives I '

serve, in turn, in the presence of a polar aprotic solvent and an imidation catalyst with a primary amine of formula VII

A-B-NH, VII

can be implemented.

Further details for carrying out this imidization reaction can also be found in Section A.3. Alternatively, the imidation can also be carried out here, as described in Section B.1.1, with relatively large amounts of amine VII in the presence of the polar aprotic solvent and of a (meth) alkali metal-containing base.

The preparation of the semicondensate I 'serving as starting material can be carried out in the customary manner by reacting the dinaphthoquaterrylenetetracarboxylic dianhydride Nc

with an aromatic diamine of the formula X.

H ₂ ND-NH ₂ X.

in the presence of a nitrogen-based compound or phenol as the solvent and a Lewis acid or piperidine as a catalyst.

The molar ratio of aromatic diamine X to dinaphthoquaterrylene tetracarboxylic acid dianhydride Nc is usually from 1.5: 1 to 1: 1, in particular from 1.2: 1 to 1:05: 1.

Nitrogen-containing heterocycles, which are preferably not further functionalized, such as quinoline, isoquinoline, quinaldine, pyrimidine, N-methylpiperidine, pyridine, pyrrole, pyrazole, triazole, tetrazole, imidazole and methylimidazole are suitable as nitrogen-basic compound. Preference is given to tertiary nitrogen-based compounds, especially quinoline.

As a rule, 5 to 200 ml, preferably 10 to 50 ml, of solvent are used per g Dinaphthoquaterrylenedukt Nc.

Suitable catalysts are Lewis acids, for example zinc compounds, especially zinc salts, such as zinc acetate and zinc chloride, and zinc oxide, inorganic and organic acids, such as hydrochloric acid, acetic acid and p-toluenesulfonic acid, with zinc acetate being preferred. Also suitable as a catalyst is piperazine, which is preferably used in combination with phenol as solvent.

Usually 0.25 to 5.0 mol, in particular 1.0 to 2.0 mol, of catalyst per mol of Nc are used.

The reaction temperature is generally 100 to 240 ^° C., preferably 160 to 240 ^° C.

It is recommended, under inert gas, for. As nitrogen or argon to work.

In general, the condensation is completed in 0.5 to 24 hours, especially 2 to 6 hours.

B.2. Preparation of dinaphthoquaterrylene derivatives of the formula Ib2

The preparation of the dinaphthoquaterrylene derivatives Ib2 is also described below in sections depending on the substituents Y.

B.2.1. Preparation of Dinaphthoquaterrylene Derivatives Ib21

The preparation of the dinaphthoquaterrylene derivatives Ib21 can be carried out by reacting the corresponding dinaphthoquaterrylene derivatives Ia1

with an aromatic diamine of the formula XI

A

H ₂ ND-NH ₂ XI

in the presence of a nitrogen-based compound or of phenol as solvent and a Lewis acid or of piperidine as catalyst.

This condensation reaction can be carried out analogously to the condensation reaction described in Section B.1.4 for the preparation of the dinaphthoquaterrylene products I '.

B.2.2. Preparation of dinaphthoquaterrylene derivatives of the formula Ib22

The preparation of the Dinaphthoquaterrylenderivate Ib22 can analogously by reaction of the corresponding Dinaphthoquaterrylenderivate Ia2

with an aromatic diamine of the formula XI

H ₂ ND-NH ₂ XI

in the presence of a nitrogen-based compound or of phenol as solvent and a Lewis acid or of piperidine as catalyst.

Further details for carrying out this condensation reaction can be taken from section B.1.4.

B.2.3. Preparation of dinaphthoquaterrylene derivatives of the formula Ib23

Also, the Dinaphthoquaterrylenderivate Ib23 are analogous by reaction of the corresponding Dinaphthoquaterrylenderivate Ia3

with an aromatic diamine of the formula XI

H ₂ ND-NH ₂ XI

in the presence of a nitrogen-based compound or of phenol as the solvent and a Lewis acid or of piperidine as a catalyst.

Further details for carrying out this condensation reaction can also be found in Section B.1.4.

B.2.4. Preparation of dinaphthoquaterrylene derivatives of the formula Ib24

As starting material for the preparation of Dinaphthoquaterrylenderivate Ib24

the corresponding dinaphthoquaterylene derivatives I 'already described in Section B.1.4

serve, which is a further condensation reaction with an aromatic diamine of the formula XI

A

H ₂ ND-NH ₂ XI

in the presence of a nitrogen-based compound or of phenol as the solvent and a Lewis acid or of piperidine as a catalyst.

This condensation reaction can again be carried out analogously to the preparation of the dinaphthoquaterrylene derivatives I '.

The dinaphthoquaterrylene derivatives I according to the invention are outstandingly suitable for use in dye-sensitized solar cells.

They show strong absorption in the wavelength range of sunlight and can cover a range from about 600 nm to about 800 nm. In order to achieve the widest possible use of the irradiated sunlight from the visible to the near-infrared region, it is advantageous to use mixtures of various Dinaphthoquaterrylenderivate I. Occasionally, it may also be advisable to use mixtures with other rylene homologs (perylenes, terrylenes, quaterrylene) or other sensitizers.

In addition, the dinaphthoquaterrylene derivatives can be advantageously combined with all the n-type semiconductors commonly used in these solar cells. Preferred examples are metal oxides used in the ceramic, such as titanium dioxide, zinc oxide, tin (IV) oxide, tungsten (VI) oxide, tantalum (V) oxide, niobium (V) oxide, cesium oxide, strontium titanate, zinc stannate, complex oxides of perovskite Type, e.g. As barium titanate, and called binary and ternary iron oxides, which may be present in nanocrystalline or amorphous form. Particularly preferred semiconductors are zinc oxide and titanium dioxide in the anatase modification, which is preferably used in nanocrystalline form.

The metal oxide semiconductors can be used alone or in the form of mixtures. It is also possible to coat a metal oxide with one or more other metal oxides. Furthermore, the metal oxides can also be used as a coating on another semiconductor, for. As GaP, ZnP or ZnS, be applied.

The nanoparticulate titanium dioxide is usually applied to a conductive substrate by a sintering process as a thin, porous, high surface area film. As a substrate are in addition to metal foils especially plastic sheets or films and glass plates in particular, which are coated with a conductive material, eg. As transparent conductive oxides (TCO), such as with fluorine or indium doped tin oxide (FTO or ITO) and aluminum-doped zinc oxide (AZO), carbon nanotubes or Metall- films are occupied.

The Dinaphthoquaterrylenderivate I can be easily and permanently fixed on the metal oxide film. The binding takes place via the anhydride function (x1) or the carboxyl groups -COOH or -COO ^" formed in situ or via the acid groups A contained in the imide or condensate radicals ((x2) or (x3)).

The Dinaphthoquaterrylenderivate I can be used in salt form. Particularly suitable are the alkali metal salts, in particular the lithium, sodium, potassium and cesium salts, and the quaternized ammonium salts, especially tetraalkylammonium salts whose alkyl radicals preferably have 1 to 8 carbon atoms, for. B. tetrabutylammonium salts.

The dicarboxylic acid salt of the dinaphthoquaterrylene derivatives I can advantageously be obtained from the anhydride form (x1) by dissolving the anhydride in tetrahydrofuran, making it alkaline with an aqueous tetraalkylammonium hydroxide or alkali metal carbonate solution, refluxing for about 1 h, in a mixture of methylene chloride and water The organic phase is separated from the aqueous phase and the methylene chloride removed in vacuo.

Due to the strong absorption of the Dinaphthoquaterrylenderivate I already thin metal oxide films are sufficient to take up the required amount Dinaphthoquaterrylenderivat. Thin metal oxide films have the advantage of reducing the likelihood of unwanted recombination processes and the internal resistance of the cell. The fixation of the Dinaphthoquaterrylenderivate I on the metal oxide films can be carried out in a simple manner by the metal oxide in freshly sintered (still warm) state for a sufficient period of time (about 0.5 to 24 h) with a solution of the respective Dinaphthoquaterrylenderivats I in a suitable organic solution - be brought into contact with medium. This can be done, for example, by immersing the substrate coated with the metal oxide in the solution of the dinaphthoquaterrylene derivative. Because of its excellent solubility, this simple procedure is suitable in particular for the dinaphthoquaterrylene derivatives I substituted by (Het) aryloxy or -thio radicals R. If combinations of different dinaphthoquaterrylene derivatives I are to be used, these can be prepared from a solution containing all dinaphthoquaterrylene derivatives or successively from different solutions be applied. The most appropriate method can be easily determined in individual cases.

As already described, the dinaphthoquaterrylene derivatives I have acidic groups at one end of the molecule which ensure their fixation on the n-type semiconductor film. At the other end of the molecule, they preferably contain electron donors Y, which facilitate the regeneration of the dinaphthoquaterrylene derivative after the electron delivery to the n-type semiconductor, and also prevent the recombination with electrons already released to the semiconductor.

In particular, the amino radicals (y1) or imide or condensate radicals (y3) or (y4) which carry (thio) ether groups or amino groups as substituents are preferred as electron-donating groups Y in addition to the (thio) ether radicals (y2). Very particular preference is given to the amino radicals (y1) and imide radicals (y3) substituted by amino groups -NR ⁷ R ⁸ .

These substituents additionally cause a bathochromic shift in the absorption and thus expand the spectral range usable by the dinaphthoquaterrylene derivatives.

The regeneration of Dinaphthoquaterrylenderivate I can finally be done both with liquid electrolytes and with solid p-type conductors.

As examples of liquid electrolytes, there may be mentioned redox systems such as iodine / iodide, bromine / bromide and hydroquinone / quinone as well as transition metal complexes which may be dissolved in a polar organic solvent, in an ionic liquid or in a gel matrix.

Examples of solid p-type conductors are inorganic solids, such as copper (I) iodide and copper (I) thiocyanate, and above all organic p-type conductors based on polymers, such as polymers. lythiophene and polyarylamines, or of amorphous, reversibly oxidizable, non-organic compounds such as the spirobifluorenes mentioned above.

Solid p-type conductors can also be used in the dye-sensitized solar cells according to the invention without increasing the cell resistance, since the dinaphthoquaterrylene derivatives I strongly absorb and therefore only require thin n-type semiconductor layers.

The dye-sensitized solar cells according to the invention are otherwise constructed as usual, so that further explanations are not required here. The basic structure of dye-sensitized solar cells is described for example in US 4,927,721 and US 5,350,644.

The dye-sensitized solar cells according to the invention can advantageously be used as an energy source for a number of applications. As an example of a particularly interesting application is the recovery of hydrogen and oxygen by electrolytic cleavage of water called.

The invention is further illustrated by the following examples.

Examples

example 1

N, N'-bis (N- (2,6-diisopropylphenyl) -1, 6,8 (9), 11,16,18-hexabromoquaterrylene-3,4: 13,14-bis (dicarboximide) 1 _, N, N'-bis (N- (2,6-diisopropylphenyl) quaterrylene-3,4: 13, 14-bis (dicarboximide) (3 g, 3.0 mmol) and bromine (65 mL, 1.26 mol) were dissolved in chloroform (1.3 L) was stirred for 60 hours at 55 ^° C. The reaction mixture was cooled to room temperature and added to a vigorously stirred solution of KOH (15 g) and NaHSO ₃ (15 g) in water (2 L ₎ The organic layer was separated, dried with anhydrous sodium sulfate and concentrated The residue was purified by column chromatography on silica gel using dichloromethane as eluant to give 3.6 g of Compound 1 as a green powder (84%). mp> 400 ^° C; ¹ H NMR (500 MHz, CD ₂ CI ₂ , 293 K): δ = 9.67 (s, 2H). 9.54 (d, 2H), 7.47 (t, 2H), 7.30 (t, 2H), 2.67 (sep, 4H), 1.02 (d, 24H), ¹³ C NMR (67 MHz, CD ₂ CI ₂ , 293 K): δ = 161.7, 161.4, 145.0, 133.5, 131.8, 129.8, 129.5, 129.1, 128.6, 128.5, 128.4, 128.3, 126.1, 125.5, 121.5, 120.9, 1 19.6, 1 19.5, 28.5, 23.1; IR (KBr): v = 2961, 2927, 2867, 1717, 1713, 1705, 1674, 1590, 1573, 1468, 1386, 1348, 1233, 1197, 1172, 1152, 1051, 842, 815, 794, 724 cm ^"1 ; UV / vis (CHCl ₃ ):

(ε) = 749 (); MS (FD, 8 kV): m / z (%): 1431.6 (100) [M ⁺ ]; Found: C, 56.07; H, 3.13; N, 1.99%. CAIC. for C ₆₈ H ₄₄ Br ₆ N ₂ O ₄ : C, 56.71; H, 3.10; N, 1.96%.

N, N'-bis (N- (2,6-diisopropylphenyl) -1,6,11,16-tetrakis (4- (1,1,3,3-tetramethylbutyl) phenoxy) -8 (9), 18 -dibromoquaterrylene-3,4: 13,14-bis (dicarboximide) 2: Compound 1 (1.43 g, 1 mmol), tert-octylphenol (0.845 g, 4 mmol) and K ₂ CO ₃ (0.3 g, 2.2 mmol) The mixture was suspended in NMP (150 ml) in a 250 ml Schlenck flask and purged with argon, and the mixture was stirred under argon for 48 hours at 110 ^° C. After allowing to cool to room temperature, the mixture was precipitated onto a mixture of 6M HCl ( The green precipitate was filtered off, washed with water and dried in vacuo Compound 2 was isolated by column chromatography on silica gel using toluene as eluent Yield 1.44 g (85%). Mp., 100 ml) and ice (200 g) > 400 ^° C; ¹ H NMR (500 MHz, CD ₂ CI ₂ , 293 K): 5 = 9.78 (s, 3H), 9.57 (d, ³ J = 8.95 Hz, 2H), 9.18 (d, ³ J = 8.80 Hz, 2H), 8.23 (s, 4H), 7.50 (m, 9H) 7.33 (d, ³ J = 7.74 Hz, 4H), 7.16 (d, ³ J = 8.65 Hz, 8H), 2.50 (sep, ³ J = 6.80 Hz, 4H), 1.70 (s, 8H ), 1.35 (s, 24H), 1.10 (d, ³ J = 6.79 Hz, 24H), 0.70 (s, 36H); ¹³ C NMR (125 MHz, CD ₂ Cl ₂ , 293 K): δ = 163.47, 155.61, 154.92, 153.74, 153.53, 153.39, 153.29, 147.42, 147.25, 147.15, 146.48, 135.95, 131.55, 120.58, 130.13, 129.81, 129.69, 129.09, 128.61, 128.58, 128.34, 127.97, 127.84, 126.00, 125.55, 124.46, 123.68, 123.40, 122.84, 122.51, 120.62, 1 19.27, 119.17, 1 18.73, 1 18.60, 1 18.55, 57.50, 38.74, 38.72, 32.65, 31.91, 31.71, 29.51, 24.13; IR (KBr): v = 2957, 1707, 1670, 1595, 1503, 1334, 1210 cm ^-1 , UV / vis (CHCl ₃ ):

nm (ε) = 779 (157900), 703 (90100); m / z {%): 1934.2 (100) [M ⁺ ]; Found: C, 86.67; H, 7.29; N, 1.50%. CAIC. for Ci ₂₄ H ₁₂₈ Br ₂ N ₂ O ₈ : C, 83.84; H, 7.38; N, 1.58%. N, N'-bis (N- (2,6-diisopropylphenyl) -1, 6,11, 16-tetrakis (4- (1, 1,3,3-tetramethylbutyl) phenoxy) -8, 9:18, 19-d / napAjfAjoquaterrylene-3, 4: 13,14-bis (dicarboximide) 3: Compound 2 (1, 94 g, 1 mmol), Pd (dba) ₂ (60 mg), P (o-tolyl) ₃ ( 30 mg), 2-Trimethylsilylphenyltriflate (1, 5 g) and CsF (460 mg) were C (in a mixture of toluene 90 ml) and acetonitrile (10 ml) stirred for 48 1 10 ⁰ h under argon. The resulting mixture was The organic layer was separated, concentrated in vacuo and purified by column chromatography on silica gel using toluene as eluent to give 0.89 g (46%) of 2 as a blue solid.

Analytical data of 2: Melting point:> 400 ^° C; ¹ H-NMR (500 MHz, C ₂ D ₂ Cl ₄ , 373 K): δ = 11.18 (s, 4H), 8.74 (br.s, 4H), 8.54 (s, 4H), 7.59 (br.s, 4H), 7:43 to 7:45 (m, 10H), 7:28 to 7:30 (m, 12H), 2.84 (sep, ³ J = 6.68 Hz, 4H), 1.71 (s, 8H), 1:38 (s, 24H), 1.10 (d , ³ J = 6.71 Hz, 24H) ppm, 0.69 (s, 36H) ppm; ¹³ C NMR (175 MHz, C ₂ D ₂ Cl ₄ , 373 K): δ = 163.37, 154.35, 154.01, 147.03, 146.18, 132.47, 131.50, 129.83, 129.51, 128.40, 128.20, 127.94, 127.68, 126.80, 125.69, 125.27, 124.18, 124.15, 123.999, 123.96, 123.91, 122.93, 122.55, 18.02, 57.59, 38.70, 32.44, 31.98, 31.63, 29.56, 24.22 ppm; IR (KBr): v = 2958, 2919, 2863, 1707, 1663, 1590, 1501, 1355, 1311, 1503, 1205, 1 160 cm ^-1 , MS (FD): m / z (rel. Int.) = 1926.1 (100%) [M ⁺ ]; Found: C, 84.74; H, 7.1 1; N, 1.50%; calculated for C i ₃₆ Hi ₃₄ N ₂ O ₈ : C, 84.88; H, 7.02; N, 1.46%; UV-Vis (toluene): λ _max (ε) = 700 (14,200), 638 (62,800), 589 (16,000), 41 1 (31,000), 389 (21,500), fluorescence (toluene): λ _max = 726 nm ( Excitation 680 nm).

Example 2

N, N'-bis (N- (2,6-diisopropylphenyl) -1,6,11,16-tetrakis (4- (1,1,3,3-tetramethylbutyl) phenoxy) -8.9: 18, 19-dinapthoquaterrylene-3,4: 13,14-tetracarboxylic monoimide monoanhydride 4: 0.70 g of compound 3 (0.36 mmol) in 200 ml of 2-methyl-2-butanol were heated to 55 ° C. After 2.0 h 0.61 g (10.8 mmol) of potassium hydroxide and 0.63 g (10.8 mmol) of potassium fluoride were added, the mixture was heated to a slight reflux (about 100 ^° C.) and stirred for 16 hours at this temperature 100 ml of 50% strength by weight acetic acid were added dropwise and the mixture was stirred for a further 1 h at 70 ^° C. The reaction product was precipitated in water, filtered off, washed with hot water and dried in vacuo dried at 100 ⁰ C. The crude product was then subjected first with toluene and with acetone as the eluent to column chromatography on silica gel. It was added 0.25 g (39%) was obtained in the form of a blue solid. 4

Analytical data of 4:

MS (FD): m / z (rel. Int.) = 1768.7 (100%) [M ⁺ ].

The saponified product N, N'-bis (N- (2,6-diisopropylphenyl) -1,6,11,16-tetrakis (4- (1,1,3,3-tetramethylbutyl) phenoxy) - 8,9: 18,19-dinaphthoquaterrylene-3,4: 13,14-bis (dicarboxylic anhydride) was not isolated.

Example 3

N, N'-bis (N- (2,6-diisopropylphenyl) -1,6,11,16-tetrakis (4- (1,1,3,3-tetramethylbutyl) phenoxy) -8.9: 18, 19-dinapthoquaterrylen-3,4-dicarboximide

5: To a nitrogen-stirred mixture of 0.55 g (0.31 mmol) of Compound 4 and 75 ml of quinoline was added 0.75 g (5.3 mmol) of copper (I) oxide. Then the mixture was heated to 210 ⁰ C and stirred for 2 h at this temperature. After thin schichtchromatographischer checking the completion of the reaction and cooling to room temperature, the reaction product on 160 g of 6 wt .-% hydrochloric acid was precipitated, filtered, washed with hot water and dried under vacuum at 100 ⁰ C. The crude product was subjected to column chromatography on silica gel with CHCl ₃ as eluent. There was obtained 0.40 g (88%) of 5 as a blue solid.

Analytical data of 5: UV-Vis (CH ₂ Cl ₂ ): λ _max = 664;

MS (FD): m / z (rel. Int.) = 1694.1 (100%) [M ⁺ ].

Example 4

N, N'-bis (N- (2,6-diisopropylphenyl) -1,6,11,16-tetrakis (4- (1,1,3,3-tetramethylbutyl) phenoxy) -8.9: 18, 19-dinapthoquaterrylene 6: To a nitrogen-stirred mixture of 0.33 g of compound 4 and the corresponding bisanhydride (0.31 mol) in 15 ml of quinoline was added 0.46 g (3.2 mmol) of copper (1). The mixture was heated to 210 ^° C. and stirred for 2 hours at this temperature. After completion of the reaction was allowed to cool to room temperature, the reaction product precipitated with 160 g of 6 wt .-% hydrochloric acid, filtered off, washed with hot water and dried in vacuo at 100 ⁰ C. The crude product was purified by column chromatography on silica gel with CHCl 3 as eluent. There was obtained 0.06 g of 6 (21%) as a blue solid.

Analytical data of 6:

MS (FD): m / z (rel. Int.) = 1464.9 (100%) [M ⁺ ].

Example 5

N, N'-bis (N- (2,6-diisopropylphenyl) -1,6,11,16-tetrakis (4- (1,1,3,3-tetramethylbutyl) phenoxy) -8.9: 18, 19-dinapthoquaterrylen-3,13-dibromquaterrylen

7: To a nitrogen-stirred mixture of 0.05 g (0.03 mmol) of 5 and 10 ml of THF was added 32 mg (0.18 mmol) of N-bromosuccinimide. Then, the mixture was heated to 70 ⁰ C and stirred for 10 h at this temperature. The reaction product was precipitated in a water / hydrochloric acid mixture (80 ml / 20 g), filtered, washed with hot water and dried in vacuo at 70 ⁰ C. The crude product was subjected to column filtration on silica gel with CH ₂ Cl ₂ as eluent. There were obtained 0.025 g of 7 as a blue solid, which corresponds to a yield of 47%.

Analytical data of 7: MS (FD): m / z (rel. Int.) = 1771, 8 (100%) [M ⁺ ].

Example 6

Use of the dinaphthoquaterrylene derivative 4 as a photosensitizer in a dye-sensitized solar cell

To test the suitability of Dinaphthoquaterrylenderivaten as photosensitizers in solar cells, solar cells were prepared as follows.

The base material used was fluoropotiated tin oxide (FTO) coated glass plates measuring 12 mm × 14 mm × 3 mm or 25 mm × 15 mm × 3 mm (Pilkington TEC 8), successively with glass cleaner, acetone and ethanol in an ultrasonic bath for 15 minutes treated, then stored in ethanol and dried in a stream of nitrogen before use.

To prepare the counter electrode 20 .mu.l of a 5 mM solution of H ₂ PtCIo in isopropanol were evenly distributed on the coated side of a FTO-glass plate with boreholes brass, and sintered after short drying in air for 30 min at 380 ⁰ C and subsequently stored free from dust.

The working electrode was prepared as follows:

From a tape, a round hole of 10 mm in diameter was punched out. Thereafter, the adhesive tape was adhered as a template to the coated side of a FTO glass plate with no holes. Then, a Tiθ ₂ paste was applied with a squeegee.

After removal of the adhesive tape and a short drying at 80 ⁰ C, the metal-oxide-coated glass plate was sintered for 30 minutes at 450 ⁰ C, then allowed to cool to 80 ⁰ C and 14 h 5 placed in toluene in a 500 mM solution of the Dinaphthoquaterrylenderivats. The glass plate taken out of the solution was rinsed with toluene and dried in a stream of nitrogen. The thickness of the Tiθ ₂ layer after sintering was 10 μm.

The glass plates (Arbeitselektorde and counter electrode) were then incubated with a 50 micron thick heat sealable film (Surlyn ^® 1702; DuPont) sealed. The space between the two electrodes was then filled through the holes with the electrolyte (0.5 M LiI, 0.25 M tetrabutylammonium iodide and 0.05 M 12 in methoxypropionitrile). After sealing the drill holes with another hot-melt adhesive, the contact surfaces of the working and counter electrodes were coated with silver conductive paint and covered with copper adhesive tape (3M).

The cell thus prepared had an active area of 0.79 cm ² .

The structure of the solar cell is shown schematically in FIG. It means:

1 glass plate

2 FTO layer

3 platinum layer

4 electrolyte layer

5 dye-impregnated TiO ₂ layer

6 FTO layer

7 glass plate

8, 9 sealing

10, 11 silver contacts

12, 13 lines

The Quantum Efficiency in% (IPCE) was then measured with a 75 watt xenon arc lamp (LOT-Oriel), a 1/8 m monochromator (SpectraPro-2150i; Acton Research Corporation), a transimpedance amplifier (Aescusoft GmbH Automation) and a lock-in amplifier 7265 (signal recovery) measured.

The current / voltage characteristic was η To determine the efficiency with a source meter Model 2400 (Keithley Instruments Inc.) under irradiation with a halogen lamp box (Xenophot ^® 64629; Osram) measured as a solar simulator at 0.1 sun. The measured IPCE curve is shown in FIG.

The measured here current / voltage curve is shown in Figure 3.

The determined efficiencies η were 1.80% for the dye 4.

FIG. 4 shows the absorption spectrum (solid line) and the emission spectrum (dashed line) of compound 3, as well as the absorption spectrum (ge). dotted line) of the precursor compound 2 (x-axis: wavelength in nm; y-axis: absorption or emission in au).

Claims

claims

1. Dinaphthoquaterrylene derivatives of the general formula I.

in which the variables have the following meaning:

X together to form a six-membered ring connected to a radical of formula (x1), (x2) or (x3)

(x1) (x2) (x3)

or both a remainder -COOM;

Y one of the two radicals is a radical of the formula (y1)

-L-NR ¹ R ² (yi)

or a radical of the formula (y2)

- L - Z - R ^J (y2)

and the other group is hydrogen; or with each other to form a six-membered ring connected to a radical of the formulas (y3) or (y4)

(y3) (y4)

or both hydrogen;

same or different radicals:

Amino -NR ¹ R ² , aryloxy, arylthio, hetaryloxy or hetarylthio, to which in each case further saturated or unsaturated 5- to 7-membered rings, whose carbon skeleton is represented by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be fused, wherein the entire ring system one or more times by the radicals (i), (ii), (iii ), (iv) and / or (v) may be substituted: (i) C 1 -C ₃₀ -alkyl whose carbon chain is represented by one or more moieties -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -OC-, -CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted and may be mono- or polysubstituted by: C _r Ci ₂ alkoxy, C _r C ₆ alkylthio, -C≡CR ⁴ , -CR ⁴ = CR ⁴ ₂ , hydroxy, mercapto, halogen, cyano, nitro, -NR ⁹ R ¹⁰ , -NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , -SO ₃ R ⁷ , -PR ⁷ ₂ , -POR ⁷ R ⁷ , (Het) aryl and / or saturated or unsaturated C ₄ -

C ₇ -cycloalkyl, whose carbon skeleton by one or more -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, where the (het) aryl and cycloalkyl radicals may each be mono- or polysubstituted by Ci-Ci ₈ alkyl and / or the above, as substituents for alkyl radicals may be substituted;

(ii) C ₃ -C ₈ -cycloalkyl whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted and to the further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is represented by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be fused, wherein the entire ring system may be mono- or polysubstituted by: C 1 -C ₈ -alkyl, C 1 -C ₂ -alkoxy, C 1 -C ₆ -alkylthio, -C≡CR ⁴ , -CR ⁴ CRCR ⁴ ₂ , hydroxyl, mercapto, halogen, cyano, nitro, - NR ⁹ R ¹⁰ , -NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , -SO ₃ R ⁷ , -PR ⁷ ₂ and / or - POR ⁷ R ⁷ ; (Iii) aryl or hetaryl to which further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more moieties -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, may be annelated, wherein the entire ring system may be mono- or polysubstituted by: Ci-Ci ₈ alkyl, ci C ₂ alkoxy, Cr

Ce-alkylthio, -C (CR ⁴ , -CR ⁴ = CR ⁴ ₂ , hydroxy, mercapto, halogen, cyano, nitro, - NR ⁹ R ¹⁰ , -NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , -SO ₃ R ⁷ , -PR ⁷ ₂ , -POR ⁷ R ⁷ , (Het) aryl, (Het) aryloxy and / or (Het) arylthio, where the (Het) aryl radicals in each case one or more times by C ₁ -C ₈ -alkyl, C ₁ -C ₂ -alkoxy, C ₁ -C ₆ -alkylthio, hydroxyl, mercapto, halogen, cyano, nitro, -NR ⁹ R ¹⁰ , -NR ⁵ COR ⁶ , - CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ ,

-COOR ⁷ , -SO ₃ R ⁷ , -PR ⁷ ₂ and / or -POR ⁷ R ⁷ may be substituted; (iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals mentioned as substituents for the aryl radicals (iii), where U is a grouping -O-, -S-, -NR ³ -, -CO-, -SO- or -SO ₂ - means; (v) C _r C ₂ alkoxy, C _r C ₆ alkylthio, -C≡CR ^4, -CR ⁴ = CR ⁴ _2, hydroxy, mercapto,

Halogen, cyano, nitro, -NR ⁹ R ¹⁰ , -NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , -SO ₃ R ⁷ , -PR ⁷ ₂ and / or - POR ⁷ R ⁷ ;

RA is hydrogen, Ci-CI8-alkyl, C _r C ₂ alkoxy, amino, -NR ¹ R ^2, phenoxy, where in each case two vicinal radicals RA to a further saturated or unsaturated

5- to 7-membered ring whose carbon skeleton interrupted by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be connected, wherein the ring system may be mono- or polysubstituted by radicals (i), (ii), (iii), (iv) and / or (v), preferably hydrogen;

B d-Cβ alkylene, C ₂ -C ₆ alkenylene, C ₂ -C ₆ alkynylene, phenylene or combinations of these bridge members, the mono- or poly-substituted by d-Ci ₂ alkyl, nitro, cyano and / or halogen or could be;

A are identical or different radicals -COOM, -SO ₃ M, -PO ₃ M or -Si (OR) ₃ , in which R is H, CH ₃ and / or C ₂ H ₅ , where n = 1 - 3;

D is phenylene, naphthylene or pyridylene, the _2-alkyl, d-C ₂ alkoxy, hydroxy, nitro and / or halogen may be substituted one or more times by d- Ci;

M is hydrogen, alkali metal cation or [NR ⁵ ₄ ] ⁺ ; L is a chemical bond or an arylene or hetarylene radical of the formulas bonded directly or via ethenylene or ethynylene to the dinaphthoquaterrylene skeleton

- Ar - - Ar - E - Ar -

in which the (het) arylene radicals Ar may be identical or different, may contain heteroatoms as ring atoms and / or have fused saturated or unsaturated 5- to 7-membered rings which may likewise contain heteroatoms, where the entire ring system is a - or multiple times

Phenyl, Ci-C _r C ⁵ R ⁶ may be substituted ₂ alkyl, Ci-C ₂ alkoxy, C ₂ -alkylthio and / or -NR;

E is a chemical bond or moiety -O-, -S-, -NR ⁴ -, -C (C-, -CR 4 = CR 4 or C 1 -C 6 -alkylene;

R 1, R 2 independently of one another are alkyl radicals (i), cycloalkyl radicals (ii) or (het) aryl radicals (iii) which are mentioned as substituents for the radicals R; linked together to a nitrogen atom-containing, saturated or unsaturated, 5- to 7-membered ring whose carbon chain may be interrupted by one or more moieties -O-, -S- and / or -NR4-, to the one or two unsaturated or saturated 4- to 8-membered rings may be anelliert whose carbon chain may also be interrupted by these groups and / or -N =, wherein the entire ring system may be mono- or polysubstituted by: C1- C24-alkyl, which is represented by C1-C18

Alkoxy, C 1 -C 18 -alkylthio and / or -NR 5 R 6, (Het) aryl which may be monosubstituted or polysubstituted by C 1 -C 18 -alkyl and / or the abovementioned radicals which are mentioned as substituents for alkyl, C18 alkoxy, C1-C18 alkylthio and / or -NR5R6;

Z is -O- or -S-;

R ^{3 is} one of the substituents for the radicals R mentioned alkyl radicals (i) or

(Het) aryl radicals (iii);

R 'is hydrogen;

C 1 -C ₃₀ -alkyl whose carbon chain is represented by one or more moieties - O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -OC-, -CR ⁴ CRCR ⁴ -, -CO- , -SO- and / or -SO ₂ - may be interrupted and may be mono- or polysubstituted by the substituents mentioned for the radicals R radicals (ii), (iii), (iv) and / or (v) ; C ₃ -C ₈ -cycloalkyl to which further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is replaced by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, - CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, the entire ring system being mono- or polysubstituted by the radicals mentioned as substituents for the radicals R ( i), (ii), (iii),

(iv) and / or (v) may be substituted;

Aryl or hetaryl, to the further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, may be annelated, wherein the entire ring system may be mono- or polysubstituted by the substituents mentioned for the radicals R radicals (i), (ii), (iii), (iv), (v) and / or aryl and / or hetarylazo, each of which may be substituted by C ₁ -C 10 -alkyl, C ₁ -C ₆ -alkoxy and / or cyano;

R ^{4 is} hydrogen or dC-is-alkyl, where the radicals R ^{4 may be} identical or different if they occur several times;

R ⁵ , R ⁶ independently of one another: hydrogen; Ci-Ci ₈ -alkyl, the carbon chain by one or more groups -

O-, -S-, -CO-, -SO- and / or -SO ₂ - may be interrupted and the one or more times by d-Ci ₂ -alkoxy, Ci-C ₆ alkylthio, hydroxy, mercapto, halogen , Cyano, nitro and / or -COOR ⁸ may be substituted; Aryl or hetaryl, to each of which further saturated or unsaturated 5- to 7-membered rings, whose carbon skeleton may be interrupted by one or more groups -O-, -S-, -CO- and / or -SO ₂ - be annelated can, wherein the entire ring system may be mono- or polysubstituted by d-Ci ₂ alkyl and / or the above, as substituents for alkyl radicals may be substituted, wherein the radicals R ^{5 may be} identical or different, if they occur more than once;

R ⁷ is C 1 -C ₈ -alkyl whose carbon chain may be interrupted by one or more groupings -O-, -S-, -CO-, -SO- and / or -SO ₂ - and which is mono- or polysubstituted by d- C ₂ alkoxy, Ci-C ₆ alkylthio, hydroxy, mercapto, halogen,

Cyano, nitro and / or -COOR ⁸ may be substituted;

Aryl or hetaryl, to each of which further saturated or unsaturated 5- to 7-membered rings, whose carbon skeleton may be interrupted by one or more groups -O-, -S-, -CO- and / or -SO ₂ - be annelated can, with the entire ring system one or more times by d-Ci ₂ alkyl and / or the substituents mentioned above as substituents for alkyl may be substituted, wherein the radicals R ^{7 may be} identical or different if they occur more than once;

R ^{8 is} Ci-Ciβ-alkyl;

R ⁹ , R ^{10 is} C 1 -C ₃₀ -alkyl whose carbon chain is represented by one or more groupings -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -OC-, -CR ⁴ = CR ⁴ -, - CO-, -SO- and / or -SO ₂ - may be substituted and which may be monosubstituted or polysubstituted by: d-

Ci ₂ -alkoxy, d-Ce-alkylthio, -C≡CR ⁴ , -CR ⁴ = CR ⁴ ₂ , hydroxy, -NR ⁵ R ⁶ , -NR ⁵ COR ⁶ , (Het) aryl and / or saturated or unsaturated C C ₄ -C ₇ -cycloalkyl whose carbon skeleton may be interrupted by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ - and / or -CR ⁴ = CR ⁴ -, where the Het) aryl and cycloalkyl radicals may each be mono- or polysubstituted by C 1 -C ₈ -alkyl and / or the abovementioned radicals mentioned as substituents for alkyl;

Aryl or hetaryl, to the further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, may be annelated, where the entire ring system may be mono- or polysubstituted by: Ci-Ci ₈ alkyl, Ci-Ci ₂ - Alkoxy, CrCβ-alkylthio, - C≡CR ⁴ , -CR ⁴ = CR ⁴ ₂ , hydroxy, -NR ⁵ R ⁶ , -NR ⁵ COR ⁶ , (Het) aryl, (Het) aryloxy and / or (Het) arylthio wherein the (het) aryl radicals ⁵ R ⁶ and / or -NR ⁵ COR ⁶ may each be mono- or polysubstituted by d-Ciβ alkyl, C _r C ₂ alkoxy, hydroxy, -NR; with the nitrogen atom bonded to a saturated or unsaturated, 5- to 7-membered ring, the carbon chain of which may be interrupted by one or more moieties -O-, -S- and / or -NR ⁴ -, to the one or two unsaturated or saturated 4- to 8-membered rings may be annealed, the carbon chain may also be interrupted by these groups and / or -N =, wherein the entire ring system may be mono- or polysubstituted by: dC ₂₄ alkyl, by dC-is-alkoxy, dC-is-alkylthio and / or -NR ⁵ R ⁶ may be substituted, (Het) aryl which is mono- or polysubstituted by C 1 -C ₈ -alkyl and / or the above, as substituents for alkyl mentioned

Residues may be substituted, Ci-Ci ₈ -alkoxy, Ci-Ci _8- Alkylthio and / or -NR ⁵ R ⁶ .

2. Dinaphthoquaterrylenderivate according to claim 1, characterized in that the variables in formula I have the following meaning: X together to form a six-membered ring connected to a radical of formula (x1) or both a radical -COOM;

Y one of the two radicals is a radical of the formula (y1) or (y2) and the other radical is hydrogen or with one another to form a six-membered ring to form a radical of the formula (y3);

R is phenoxy or thiophenoxy, which may each be monosubstituted or polysubstituted by identical or different radicals (i), (ii), (iii), (iv) and / or (v):

(i) C 1 -C 6 -alkyl whose carbon chain is represented by one or more groups -O-, -S-, -NR ⁴ -, -C≡C-, -CR ⁴ CRCR ⁴ - and / or -CO- and / or - SO ₂ - may be interrupted and may be mono- or polysubstituted by d-C ₂ alkoxy, hydroxy, halogen, cyano and / or aryl which is monosubstituted or polysubstituted by Ci-Ci ₈ alkyl or C -C ₆ alkoxy may be substituted;

(ii) C ₃ -C ₈ -cycloalkyl, whose carbon skeleton may be interrupted by one or more moieties -O-, -S-, -NR ⁴ -, -CR ⁴ = CR ⁴ - and / or -CO-, and the - or may be substituted several times by Ci-Ci ₈ -alkyl, d-Ci ₂ -alkoxy and / or dC ₆ -alkylthio;

(iii) aryl or hetaryl, to which in each case further 5- to 7-membered saturated or unsaturated rings whose carbon skeleton is replaced by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, - CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be annelated, where the entire ring system may be mono- or polysubstituted by: d-ds-alkyl, C ₁ -Ci ₂ -alkoxy, -C≡CR ⁴ , -CR ⁴ = CR ⁴ ₂ , hydroxy, halogen, cyano, - NR ⁹ R ¹⁰ , -NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , -SO ₃ R ⁷ , (Het) aryl, (Het) aryloxy and / or (Het) arylthio, where the (het) aryl radicals are in each case mono- or polysubstituted by C 1 -C ₈ -alkyl, Ci ₈ alkoxy and / or cyano can be substituted tuiert;

(iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals which are mentioned as substituents for the aryl radicals (iii), where U is a grouping -O-, -S-, -NR ⁴ -, -CO-, -SO- or -SO ₂ -; (V) Ci-C ₂ alkoxy, C _r C ₆ alkylthio, -C≡CR ^4, -CR ⁴ = CR ⁴ _2, hydroxyl, mer- capto, halogen, cyano, nitro, -NR ⁹ R ^10, - NR ⁵ COR ^6, -CONR ⁵ R ^6, - SO ₂ NR ⁵ R ^6, -COOR ⁷ and / or -SO ₃ R ^7;

RA hydrogen.

3. Dinaphthoquaterrylenderivate according to claim 1, characterized in that the variables in formula I have the following meaning:

X together to form a six-membered ring joined to a group of formula (x2) or (x3);

Y one of the two radicals is a radical of the formula (y1) or (y2) and the other radical hydrogen or with each other to form a six-membered ring to form a radical of the formula (y3) or (y4) or both hydrogen;

R is phenoxy or thiophenoxy, which may each be monosubstituted or polysubstituted by identical or different radicals (i), (ii), (iii), (iv) and / or (v): (i) C 1 -C 30 -alkyl, whose carbon chain can be interrupted by one or more groups -O-, -S-, -NR ⁴ -, -C≡C-, -CR ⁴ = CR ⁴ - and / or -CO- and / or -SO ₂ - and may be mono- or polysubstituted by d-C ₂ alkoxy, hydroxy, halogen, cyano and / or aryl which may be mono- or polysubstituted by Ci-Ci ₈ alkyl or Ci-C ₆ alkoxy ;

(ii) C ₃ -C ₈ -cycloalkyl, whose carbon skeleton may be interrupted by one or more moieties -O-, -S-, -NR ⁴ -, -CR ⁴ = CR ⁴ - and / or -CO-, and the - or may be substituted several times by Ci-Ci ₈ -alkyl, d-Ci ₂ -alkoxy and / or dC ₆ -alkylthio; (iii) aryl or hetaryl, to which in each case further 5- to 7-membered saturated or unsaturated rings whose carbon skeleton is replaced by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, - CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be annelated, where the entire ring system may be mono- or polysubstituted by: d-ds-alkyl, C ₁ -Ci ₂ -alkoxy, -C≡CR ⁴ , -CR ⁴ = CR ⁴ ₂ , hydroxy, halogen, cyano, -

NR ⁹ R ¹⁰ , -NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , -SO ₃ R ⁷ , (Het) aryl, (Het) aryloxy and / or (Het) Arylthio, where the (het) aryl radicals may each be mono- or polysubstituted by C 1 -C ₈ -alkyl, C 1 -C ₈ -alkoxy and / or cyano; (iv) a radical -U-aryl, which is mono- or polysubstituted by the above, as

Substituents for the aryl radicals (iii) may be substituted, wherein U represents a grouping -O-, -S-, -NR ⁴ -, -CO-, -SO- or -SO ₂ -; (V) Ci-Ci ₂ -alkoxy, Ci-C ₆ alkylthio, -C (CR4, -CR 4 = CR42, hydroxy, mer- capto, halogen, cyano, nitro, -NR9R10, -NR5COR6, -CONR5R6, - SO2NR5R6 , -COOR7 and / or -SO3R7;

RA hydrogen.

4. Dye-sensitized solar cells containing at least one Dinaphthoquaterrylende- derivative of formula I according to any one of claims 1 to 3 as photosensitizers.

5. Use of the Dinaphthoquaterrylenderivate of formula I according to any one of claims 1 to 3 as photosensitizers in solar cells.

6. Dinaphthoquaterrylenbis (dicarboximide) e of the general formula II

in which the variables have the following meaning:

R same or different radicals:

Amino -NR ¹ R ² , aryloxy, arylthio, hetaryloxy or hetarylthio, to which in each case further saturated or unsaturated 5- to 7-membered rings, whose carbon skeleton is represented by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be fused, wherein the entire ring system one or more times by the radicals (i), (ii), (iii ), (iv) and / or (v) may be substituted:

(i) C 1 -C 30 -alkyl whose carbon chain is represented by one or more moieties -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -C≡C-, -CR ⁴ = CR ⁴ -, -CO -, -SO- and / or -SO ₂ - may be interrupted and may be mono- or polysubstituted by: Ci-Ci ₂ -alkoxy, C _r C ₆ alkylthio, -C≡CR ⁴ , -CR ⁴ = CR ⁴ ₂ , hydroxy, mercapto,

Halogen, cyano, nitro, -NR ⁹ R ¹⁰ , -NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , - SO ₃ R ⁷ , -PR ⁷ ₂ , -POR ⁷ R ⁷ , (Het) aryl and / or saturated or unsaturated C ₄ -C ₇ -cycloalkyl, whose carbon skeleton is represented by one or more groups -O-, -S-, - NR ⁴ -, -N = CR ⁴ -, CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, wherein the (het) aryl and cycloalkyl radicals in each case one or can be substituted several times by dC-is-alkyl and / or the above mentioned as substituents for alkyl radicals;

(ii) C ₃ -C ₈ -cycloalkyl whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted and to the further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, the entire ring system may be mono- or polysubstituted by Ci-Ci ₈ alkyl, d-C ₂ alkoxy, -C ₆ - alkylthio, -C≡CR ^4, -CR ⁴ = CR ⁴ _2, hydroxy, mercapto, halogen, cyano, nitro, - NR ⁹ R ^10, - NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , -SO ₃ R ⁷ , -PR ⁷ ₂ and / or -

POR ⁷ R ⁷ ;

(Iii) aryl or hetaryl to which further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more moieties -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, may be annelated, wherein the entire ring system may be mono- or polysubstituted by: Ci-Ci ₈ alkyl, ci Ci ₂ alkoxy, d-Ce-alkylthio, -C≡CR ⁴ , -CR ⁴ = CR ⁴ ₂ , hydroxy, mercapto, halogen, cyano, nitro, - NR ⁹ R ¹⁰ , -NR ⁵ COR ⁶ , -CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , -SO ₃ R ⁷ , -PR ⁷ ₂ , -POR ⁷ R ⁷ , (Het) aryl, (Het) aryloxy and / or (Het) arylthio, wherein the (het) aryl groups may each be mono- or polysubstituted by Ci-Ci ₈ alkyl, _Ci-Ci2 alkoxy, Ci-C ₆ alkylthio, hydroxy,

Mercapto, halogen, cyano, nitro, -NR ⁹ R ¹⁰ , -NR ⁵ COR ⁶ ,

-CONR ⁵ R ⁶ , -SO ₂ NR ⁵ R ⁶ , -COOR ⁷ , -SO ₃ R ⁷ , -PR ⁷ ₂ and / or -POR ⁷ R ⁷ may be substituted; (iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals mentioned as substituents for the aryl radicals (iii), where U is a grouping -O-, -S-, -NR ³ -, -CO-, -SO- or -SO ₂ - means; (v) Ci-C ₂ alkoxy, C _r C ₆ alkylthio, -C≡CR ^4, -CR ⁴ = CR ⁴ _2, hydroxy, mercapto, halogen, cyano, nitro, -NR ⁹ R ^10, -NR ⁵ COR ^6, -CONR ⁵ R ^6, -SO ₂ NR ⁵ R ^6, -COOR ^7, - SO ₃ R ^7, -PR ⁷ ₂ and / or -POR ⁷ R ^7;

Hydrogen;

CrC ₃ o-alkyl, whose carbon chain is represented by one or more moieties - O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -C≡C-, -CR ⁴ = CR ⁴ -, -CO -, -SO- and / or -SO ₂ - may be interrupted and the mono- or polysubstituted by the substituents mentioned for the radicals R radicals (ii), (iii), (iv) and / or (v) be substituted can; C ₃ -C ₈ -cycloalkyl to which further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is replaced by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, - CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, the entire ring system being mono- or polysubstituted by the radicals mentioned as substituents for the radicals R ( i), (ii), (iii),

(iv) and / or (v) may be substituted;

Aryl or hetaryl, to the further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, CR ⁴ = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, may be annelated, wherein the entire ring system may be mono- or polysubstituted by the substituents mentioned for the radicals R radicals (i), (ii), (iii), (iv), (v) and / or aryl and / or hetarylazo, each of which may be substituted by C ₁ -C 10 -alkyl, C ₁ -C ₆ -alkoxy and / or cyano.

RA is hydrogen, C 1 -C ₈ -alkyl, C ¹ -C ₂ -alkoxy, amino -NR ¹ R ² , phenoxy, where in each case two vicinal radicals R A form a further saturated or unsaturated 5- to 7-membered ring, whose carbon skeleton is replaced by one or more Groupings -O-, -S-, -NR ⁴ -, -N = CR ⁴ -, -CO-, -SO- and / or -SO ₂ - may be connected, wherein the ring system one or more times may be substituted by the radicals (i), (ii), (iii), (iv) and / or (v)

7. peri-Halogendinaphthoquaterrylendicarbonsäureimide of the general formula IIb

in which the variables R, R 'and RA are as defined in claim 6.