AU2011346645B2 - Naphtalene monoimide derivatives and use thereof as photosensitizers in solar cells and photodetectors - Google Patents

Naphtalene monoimide derivatives and use thereof as photosensitizers in solar cells and photodetectors Download PDF

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AU2011346645B2
AU2011346645B2 AU2011346645A AU2011346645A AU2011346645B2 AU 2011346645 B2 AU2011346645 B2 AU 2011346645B2 AU 2011346645 A AU2011346645 A AU 2011346645A AU 2011346645 A AU2011346645 A AU 2011346645A AU 2011346645 B2 AU2011346645 B2 AU 2011346645B2
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Ingmar Bruder
Felix Eickemeyer
Neil Gregory Pschirer
Helmut Reichelt
Jan Schoneboom
Rudiger Sens
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Abstract

Provided are compounds of the formulae la and lb, in which the variables R, n, A, B, R

Description

Naphthalene monoimide derivatives and use thereof as photosensitizers in solar cells and photodetectors
Description
The present invention relates to compounds of the formulae la and lb in which
R are identical or different aryloxy, arylthio, hetaryloxy or hetarylthio radicals, n is 0, 1,2, 3, 4 or 5, B is Ci-C6-alkylene or 1,4-phenylene, where the phenylene radical may be mono- or polysubstituted by alkyl, nitro, cyano and/or halogen, A is -COOM, -SO3M or -PO3M, M is hydrogen, an alkali metal cation or [NR'4]+, R' is hydrogen or alkyl, where the R' radicals may be the same or different, L is a bridge of the formula
which may be mono- or polysubstituted by phenyl, alkyl, alkoxy, alkylthio and/or -NR4R5, and in which Ar is aryl or hetaryl which may be fused to saturated or unsaturated 5- to 18-membered rings which may comprise heteroatoms which may be the same or different in the case of two or three Ar, R4, Rs at® each Indspenderrtly hydrogen, alkyl whose carbon chain may be interrupted by one or more -0-, -S- -CO, -SO- and/or -SGa- moieties, aryl or heteryl, each of which may be mono- or polysubstituted by alkyl, alkoxy and/or sikyithio, R’, R2 are each independently radicals of the formula Ha or lib
Ob) (fib)
Rs Is phenyl, alkyl, alkoxy, aikylihio or -NFPR®, m is Q, 1,2,, 3 or 4, X is C(RWi3, NR8, oxygen or sulfur and R®, R7, R8 are each independently hydrogen, alkyl whose carbon chain may be interrupted by one or more -G-, -S-, -CO, -SO- and/or -SO*- moieties, aryl or heiaryf, each of which may be mono- or poiysubstifuted by alkyl, alkoxy and/or alkylthio.
The present invention further relates to the use of compounds of the formula la or ib or mixtures of compounds of the formulae ia and ib and/or Isomers or mixtures of the isomers of the compounds of the formulae la and ib as photosensftizers In solar ceils and photodetectors, and to solar cels and photodectors which comprise such compounds of the formula ia or ib or mixtures of compounds of the formulae la and Ib and/or isomers or mixtures of the isomers of the compounds of the formulae la and Ib as photosensitizers.
The direct conversion of solar energy to electrical energy in solar ceils is based on the internal photoeffect of a semiconductor material, Le. the generation of electron-hole pairs by absorption of photons and the separation of the negative and positive charge carders at a. p-n junction or a Schotfky contact. The phoiovoltege thus generated can bring about a phofocurrent in an external circuit, through which the soiar cel del vers its power.
The semiconductor can absorb only those photons which have an energy which is greater than its band gap. The size of the semiconductor band gap thus determines the fraction of sunlight which can be converted to electrical energy.
Thin layers or films of metal oxides are known to constitute inexpensive solid semiconductor materials (n-sem[conductors), but their absorption, owing to large band gaps, is typically not within tine visible region of the electromagnetic spectrum. For use in solar cells, the metal oxides therefore have to be combined with a photosensifeer which absorbs In the wavelength range of sunlight, Le. at from 3GG to 2000 rim, and, in the electronically excited state, injects electrons into the conduction band of the semiconductor. With the aid of a redox system which Is used additionally in the cejf and is reduced at the counterelectrode, electrons are recycled to the sensitizer which Is thus regenerated.
Of particular Interest for use in solar cells are the semiconductors sine oxide, tin dioxide and especially titanium dioxide, which are used In the form ofnanocrysteliie porous layers. These layers have a large surface area which is coated with the sensitizer, so that high absorption of sunlight is achieved.
Dye-sensitized solar cells which are based on titanium dioxide as the semiconductor material are described, for example, in US-A-4 927 721, Nature 353, p, 737-740 (1991) and US-A-5 350 544, and also Nature 395, p. 533-585 (1998) and EP-A-1 178 646, These solar cells comprise monomolecufar films of transition metal complexes, especially ruthenium complexes, which are bonded to the titanium dioxide layer via acid groups, as sensitizers and iorilne/lodiete redox systems present in dissolved form or amorphous organic ^conductors based on spirobifluorsnes.
Also proposed repeatedly as sensitizers, not least for reasons of cost, have been metal-free organic dyes.
For example, US-A-6 359 211 describes, for this purpose, cyanine, oxazlne, thlazine and acridine dyes which have carboxyl groups bonded via an aikyiene radical for securing to foe titanium dioxide semiconductor, P©ryiene-3T4:9,1G-'tetracarboxyiic acid derivatives as sensitizers are examined in Japanese documents JP-A-10-183065,2000-243463,2001-093580,2000-100484 and 10-334954, and in New J, Chem, 26, p. 1155-1160 (2002), The liquid electrolyte solar cels based on these perylene derivatives, however, exhibited much lower efficiencies than a solar cell sensitized with a ruthenium complex for comparison.
The most extensively examined sensitizers at present include dyes which possess a cyanoacrylate anchor group. For example, Kim, S,; Lee, J.K.; Kang, S.Q.; Yum, j.H.; Fantecd, S.;: DeAngelis, F.; Dl Cense, D.; Nazeerruddin, M,K; Graizef, ML JAGS 2006,128,16701 examines the compound \ JK2
and Solar Energy Materials & Solar Cells £009, 93,1143 examines the compound
According to Solar Energy Materials & Solar Cells 2009,93,1143, however, the cyanoacrylate anchor groups are not sufficiently stable; decarboxylation of these dyes was found and it was suspected that, the anchor groups are unstab!© to light.
Dyes with naphthalene monoimide anchor groups are described in the document WO 2008/132103 At, but these compounds absorb In the short-wave spectral region of sunlight (absolute maximum at about 450 nm) and are therefore unsuitable for efficient absorption and conversion of sunlight.
It has now been found that, surprisingly, compounds of the formulae la and lb of the present invention which comprise naphthalene monoimide groups as anchor groups exhibit good to very good quantum efficiencies with very good stabilities in dye solar cells.
Accordingly, the compounds of the formulae la and lb detailed at the outset have been found, as has the use thereof as photosensitizers in solar cells and photodetectors.
In one aspect, the present invention provides a compound of the forumula la, lb or l*b
in which R are identical or different aryloxy, arylthio, hetaryloxy or hetarylthio radicals, n is 0, 1, 2, 3, 4 or 5, B is Ci-C6-alkylene or 1,4-phenylene, where the phenylene radical may be mono- or polysubstituted by alkyl, nitro, cyano and/or halogen, A is -COOM, -S03M or -P03M, M is hydrogen, an alkali metal cation or [NR'4]+, R' is hydrogen or alkyl, where the R' radicals may be the same or different, L is a bridge of the formula
which may be mono- or polysubstituted by phenyl, alkyl, alkoxy, alkylthio and/or -NR4R5, and in which Ar is aryl or hetaryl which may be fused to saturated or unsaturated 5- to 18-membered rings which may comprise heteroatoms which may be the same or different in the case of two or three Ar, R4, R5 are each independently hydrogen, alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -C0-, -SO- and/or-SO2- moieties, aryl or hetaryl, each of which may be mono- or polysubstituted by alkyl, alkoxy and/or alkylthio, R1, R2 are each independently radicals of the formula lla or Mb
(I la) (Mb) R3 is phenyl, alkyl, alkoxy, alkylthio or -NR7R8, m is 0, 1,2, 3 or 4, X is C(R6R7)2, NR8, oxygen or sulfur and R6, R7, R8 are each independently hydrogen, alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -C0-, -SO- and/or -SO2- moieties, aryl or hetaryl, each of which may be mono- or polysubstituted by alkyl, alkoxy and/or alkylthio.
In the context of the present invention, aryl is an aryl radical, unit or group, especially a radical with a base skeleton of 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, which is formed from one aromatic ring or a plurality of fused aromatic rings. Suitable base skeletons are, for example, phenyl, benzyl, naphthyl, anthracenyl or phenanthrenyl. This base skeleton may be unsubstituted, which means that all carbon atoms which are substitutable bear hydrogen atoms, or substituted at one, more than one or all substitutable positions of the base skeleton. Suitable substituents are, for example, alkyl radicals, preferably alkyl radicals having 1 to 8 carbon atoms, more preferably methyl, ethyl, i-propyl ort-butyl, aryl radicals, preferably C6-aryl radicals, which may in turn be substituted or unsubstituted, heteroaryl radicals, preferably heteroaryl radicals which comprise at least one nitrogen atom, more preferably pyridyl radicals, alkenyl radicals, preferably alkenyl radicals which bear a double bond, more preferably alkenyl radicals with one double bond and 1 to 8 carbon atoms, or groups with donor or acceptor action. Groups with donor action are understood to mean groups which have a +l and/or +M effect, and groups with acceptor action are understood to mean groups which have a -I and/or -M effect. Suitable groups with donor or acceptor action are halogen radicals, preferably F, Cl, Br, more preferably F, alkyl radicals, alkoxy radicals, aryloxy radicals, carbonyl radicals, ester radicals, amine radicals, amide radicals, CH2F groups, CHF2 groups, CF3 groups, CN groups, thio groups or SCN groups. The aryl radicals most preferably bear substituents selected from the group consisting of methyl, ethyl, /iso-propyl, /7-propyl, /7-butyl, /so-butyl, tert-butyl, aryloxy, amine, thio groups and alkoxy, or the aryl radicals are unsubstituted. The aryl radical or the aryl group is preferably a phenyl radical which is optionally substituted by at least one of the aforementioned substituents. The phenyl radical more preferably has none, one, two or three of the aforementioned substituents.
In the context of the present invention, heteroaryl is a heteroaryl radical, unit or group, a radical which has 5 to 30, preferably 5 to 18, carbon atoms and/or heteroatoms and differs from the aforementioned aryl radicals in that at least one carbon atom in the base skeleton of the aryl radicals is replaced by a heteroatom. Preferred heteroatoms are N, O and S. Most preferably, one or two carbon atoms of the base skeleton of the aryl radicals are replaced by heteroatoms. The base skeleton is especially preferably selected from systems such as pyridyl, pyrimidyl, pyrazyl and triazolyl, and five-membered heteroaromatics such as pyrrole, furan, thiophene, imidazole, pyrazole, triazole, oxazole and thiazole. The base skeleton may be substituted at one, more than one or all substitutable positions of the base skeleton. Suitable substituents are the same as have already been mentioned for the aryl groups.
In the context of the present Invention, the aryioxy,. arylthio, hetaryioxy and heiarylthio radicals derive in a formal sense from the aforementioned aryl and heteroaryl radicals by attachment of an oxygen or sulfur atom to a carbon atom of the aryl or heteroaryl radical.
In the context of the present Invention, alkyl is an alkyl radical, unit or group, especially a radical having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. This alkyl radical may be branched or unbranched and optionally be interrupted by one or more -Q-, -S-, ·ΌΟ~, -SG-and/or -SOg- moieties. Alkyl is more preferably selected from the group consisting of methyl, ethyl, hpropyi, n-propyl, i-butyf, n-butyl, t-butyl, sec-butyl, i-peniyl, n-peniyl, sec-peniyi, neopentyi, n*hexyl, i-hexyS and sec-hexyl.
In the context of the present Invention, aikoxy and aUcyHhio radicals derive In a formal sense from the aforementioned alkyl radicals by attachment of an oxygen or suffer atom to a carbon atom of the alkyl radical
In the context of the present invention, halogen is preferably F, Cl or Br, more preferably F, in the context of the present invention, alkali metal cation Is preferably U, Na, Cs or K, more preferably Ha.
When the bridge L is mono- or poiysubstifuted by phenyl, alkyl, aikoxy, aikylthio and/or -NR4R5, this means that these substituents are attached to suitable positions on the aromatic and heferoaromatfc Ar groups.
When the bridge L comprises two or three Ar, they may be the same or different
Examples of suitable Ar include 1,4-, 1,3- and 1,2-phenylene, 1,4-and Ι,δ-naphthyfene, 1,4-and 2,3-pyrrylene, 2,5-, 2,4- and 2,3-thienylene, 2,5-, 2,4- and 2,3-furenylene, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-and 3,5-pyridlnylene, 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-lsoquinoJinylene, 1,4-t2,5-dl(tert-butyl)Jphenylene, 1,4-(2,5-dihexyDphenylene, 1,4-[2,5-dKteri-octyi)]phenyi®ne, 1,4-(2,5-dldodecyf)phenylene and 1,4-(2,5-<S(2-dodecyi)]phenylene. Especially useful as Ar are 1,4-phenyiene and 2,5-thlenylene.
Suitable bridges L are, for example:
preferably:
Preference is given to inventive compounds in which, in the formulae la and fb; R are identical or different aryloxy or arylthio» especially phenoxy or phenyithlo, radicals, n is 0,1 or Ξ, B is CrC^Kylene, specialty
A is -Ο-ΟΟ M M is hydrogen or an alkali metal cation, - L Is a bridge of the formula
which may b® mono- or polysubstitufed by phenyl, Gi-Cia-alkyl, Ct-Cira&amp;oxy, Ci-
Cii-sSkytthio and/or -NR^R5, and in which Arte identical or different ary! or hetetryi which may be fused to saturated or unsaturated 5- to 18-membsred ring® which may comprise heteroatoms, R4, Rs are each independently hydrogen, C-rCtt-aikyl whose cartoon chain may be interrupted by one or more -0-, -5-, -C0-, -SO- and/or -SQr moieties,
Rf, R* are each independently radicals of the formulae il'a and I ! 'b
{U'a) (li'b) R3 teCrCiiralkoxy, m is 0 cr 1, X is C{RsR7)a, NR8, oxygen or sulfur and
Ra, R7t R8 are each Independently hydrogen, CrCi2-alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO", -SO- and/or -SOs- moieties.
Particular preference is given to Inventive compounds in which, In the formulae ia and Eb, n is 0, B is GrCraikytene, especially -€H«- and -<CHa)r. A is -COOM, M is hydrogen or an alkali metal cation, L is a bridge of die formula
in which Ar is identical or different aryl or f setary I, R \ R? are each independently radicals of the formulae ii a and tl'b
(H a) (H'b) R3 feCi-G^-slkoxy, rn is 0 or 1,. X is G(RsR7}s and
Re, R? are each independently hydrogen or G-rCss-aikyi.
The invention shali encompass not only the compounds of the formulae la and Sb and the preferred embodiments thereof, but also mixtures thereof; the isomers thereof and the mixtures of the isomers.
For example, the invention also includes isomeric compounds of the formula i*b shown below:
Examples
Example 1:
la
The preparation (according to Ko et al, Chemical Comm uni cations, 2004, 88-69} proceeded from (4~bromophenyi)bis{9;,9-dimethyS"9H-ffuoreri-2-yi}amines which was first reacted with th fopbene-2,5-diboronic ester
(step a). This was followed by the coupling with the methyl ester of N-(2-ca rboxyethyl)-4-chloronaphthalimids and deproteciion of the ester group (step b).
Step a): A mixture of 1.66 g (2.98 mmol) of (4-bramdphenyl)bts(9!9-dimethyI-9H“fluoren-2-yi)amlnes 2,00 g {5.98 mmol) of th iophene-2,5-diboronic ester, 0,82 g (5,96 mmol) of KsCGa dissolved In 5,2 mL of 10:1 HsO/ethanol, 92 mg (0,08 mmoi) of Pd(PPh8>4 and 10 mL of toluene was heated to 88*0 under nitrogen and stirred at this temperature for 4 h.
After coolings the reaction mixture was filtered off with suction. The mother liquor was extracted by shaking with dichfororoethane/HgQ, The solvent was removed from the organic phase and the residua was dried. The crude product was used un purified In the next reaction step.
Step b): A mixture of 2,00 g of stage a crude product, 133 g (4.3S mmol) of the methyl ester of N-(2-carboxyethylM-chloranaphthaiimide, 50,4 mg (0.055 mmol) of Pd2{dba)3,143 g (4.38 mmol) of C32CG3,26.3 mg (0,13 mmol) of iributylphosphine and dioxane was heated to 90°C and stirred at this temperature for 6 h, Alter cooling, the reaction mixture was filtered off with suction and. then the solvent was removed from the mother liquor. The crude product was purified by column chromatography with n-hexane/ethyl acetate (2:1). 70 mg of the protected compound were obtained',
The tatter was stirred with 200 mg of KOH in 10 mL of 1:1 deminerafed watsriTHF at 60‘C for one day. After cooing, 10 mL of cone. HCt were added and the mixture was stirred for 1 h, Then the reaction mixture was added to demineralized water. The solid was filtered off with suction, washed with hot demineralized water and dried.
The purification was effected by column chromatography with the eluent 10:1 dichloromethanetethano! + 2% trimethylamine. The sold obtained was extracted by stirring with 50% acetic acid at 60« C, filtered off with suction and washed with hot demineralized water. After drying,. 1 ,.2 g of a red solid were obtained,
Analytical data Ή NMR (500MHz, COCI3, 25*C): S = 8,79 (d, IN); 6,68 (d,1H); 8.63 (d, 1H); 7.88 (d, 1H); 7.80 <q, 1Ή), 7.68 (d, 2H); 7.63 (d, 2H); 7.58 (d, 2H); 7.40 (t, 3H); 7.33 (m, 3H); 7.27 (m, 4H); 7.23 (d, 2H); 7.15 (d, 2H); 5.Q2 (s, 2H); 1,43 (s, 12H)
Example 2:
2a
The preparation (according to Ko et ai„ Chemical Communications, 2004,68-69) proceeded from (4-bromophenyl)bis(9s9"dimethyi“9H“fuorer(-2'y1)amine:f which was first reacted with 2S2-histhtophene-B-boronie ester (step a). This was foiiowed by the bromination (step b) and then the coupling with the 4-boronic ester naphthaiimide of the structure
and cfeprotactbn of the ester group (step c).
Step a: A mixture of 1.67 g (3.00 mmol) of (^bromophenyObisiS^methyl-eH-fluoren^yOamine, 1.60 mL (3,00 mmol) of 5 molar NaOH and 10 ml of dloxane was degassed with argon for 30 min. Then 54 mg {0.160 mmol) of Pd[P(iBu)3]g and 100 g (3.42 mmol) oF2,2-blsthlophene-5-bororsic ester
were added,, and the mixture was heated to 85*0 and· stirred over the weekend.. After cooling, the reaction mixture was added to ice-water. Subsequently, it was extracted with dichioram ethane and the solvent was removed from the organic phase. The residue was dissolved In a little tefrahydrofuran. Methanol was added thereto until a solid precipitated out. The latter was filtered off with suction, washed with a little methanol and dried. 1.40 g of a yellow solid were obtained, which corresponds to &amp; yield of 73%.
Analytical data: Ή NMR (500MHz, DMSO, 25aC): 8 = 7,77 (m, 4H); 7.62 (d, 2H); 7.51 (d, 3H); 7.41 (d, 1H); 131 (m, 8H); 7.11 (m, 3H); 7.05 (d, 2H}; 137 (s, 12H)
Step b: A solution of 466 mg (2,62 mmol) of N-bromosuccimide and 10 ml of DWF was added dropwlse at 0-5ffG to a mixture of 1.40 g (2.18 rrtmoi) of stage a and 20 mL of dlmethylformamide (DMF). Stirring was then continued at this temperature for 15 min and then 10 mL of dilute sodium thiosulfate solution were added. The reaction mixture was added to 150 mL of demineralized water and extracted with methyl tert-bulyi ether (MTBE), The solvent was removed from the organic, phase and the residue was dried. 1.20 g of a yellow solid were obtained, which corresponds· to a yield of 76%..
Analytical data: lH NMR (500MHz, DMSO, 25aC): 8 “ 7.77 (m, 4H); 7.62 (d, 2H); 7.51 (d, 2H); 7,.42 (d, 1H); 7,31 (m; 7H>; 7..23 (d, 1H); 7.17 (d, 1H); 7.11 (df 2H); 7,06 (d, 1H); 1.37 (s, 12H)
Step c: A mixture of 100 g (1.4 mmol) of stage b, 0.84 mL (4,2 mmol) of 5 molar NaOH and 15 mL of dloxane was degassed with argon Sir 30 min. Then 24 mg (0,05 mmol) of Pd[P(©u)aj2 and 0,97 g (16 mmol) of th© 4-boron ic ester naphihaiimkte (65%) shown above were added, and the mixture was heated to 85®C and stirred for 1 day. After cooling, the reaction mixture was added to ice-water and extracted with dlchforornethane. The solvent was removed from the organic phase. The residue was purified by means of column chromatography with the eluent 4:1 didiioromethane:methanoS.
Protected targe? product was obtained, which was stirred with 1:1 THRwaier and 1 g of KOH at 65°C overnight Aier cooling, the reaction mixture was added to water, and 15 ml of cone, HO were added. The mixture was stirred at room temperature for 1 h. Then the solid was filtered off with suction, washed and dried. The crude product was purified by means of column chromatography with tine eluent 4:1 dichloromethanmmeihaooiL This gave 330 mg of a red solid, which corresponds to a yield of 28%,
Analytical data: *H NMR (500MHz, DMSO, 25*C): S = 8.80 (d, 1H); 8.61 (d, 1H); 8-55 (d, 1H); 7.99 (q. 2H): 7.76 (g, 4H); 7.65 (d, 2H); 7.56 (qt 2H); 7.51 (d, 2H); 7.47 <d, 2H); 7.30 (m, 6H); 7.12 (ds 2H); 7.06 (d, 2H); 4.75 (s,2H); 1.34 (s, 12H)
Example 3:
3a
The preparation proceeded from diarylamine, which was first reacted with bisthiophene-S-boronic ester (step a). This was followed by bromination (step b) and then coupling with 2-boro nic ester naphthalfmide (step c):
Step a: A mixture of 1.80 g {2,9 mmol) of diarylamine, 15 mL of dioxao© and 1.74 mL (8.7 mrool) of S molar NaOH was degassed with argon for 30 min. Then 51 mg (0,1 mmol) of Pd(P(tBu)3]2 and 0.,91 g (3,. 11 mmol) of bisthiophene~5-boronic ester were added, and the mixture was heated to 85*0 and stirred over the weekend. After oooiing, the reaction mixture was added to foe-water and extracted with dtohioramethane, The solvent was removed from the organic phase, and the residue was dissolved in a little THF and methanol was added. The precipitated solid was filtered off with suction and dried, The purification was effected by means of column chromatography with the eluent rehexane + 2% ethyl acetate. This gave 1.70 g of a yellow solid, which corresponds to a yield of 85%.,.
Analytical data: 1H NMR (500MHz, DMSQ, 25 *C): δ - 7,41 (d, 4H); 7,34 (d, 2H); 7.2:8 (d, 1H); 7.14 (d, 1H}; 7,08 (d, 1H); 7,04 (d, 1H); 6.99 (d, 2H); 8,86 (d, 3H); 6.81 (d, 2H); 6,70 (d, 2H); 6.65 (d, 2H); 3.58 (s, 6H); 1.11 (s, 12H)
Step b: A solution of 490 mg (2,40 mmol) of N-bramosucdmide and 10 ml of DMF was addled drepwise at 0-5*C to a mixture of 1 ..6 g (2.3 mmol) of stage a and 30 mL of DMF. Stirring was then continued at this temperature for 15 min and then 10 ml of dilute sodium thiosulfate solution were added. The reaction mixture was added to 150 mL of demineralized water. The solid was filtered off with suction, washed and dried. 1.62 g of a yeliow solid were obtained, which corresponds to a yield of 90%.
Analytical data: 1H NMR (500MHz, DMSO, 25eC): δ - 7.68 (d, 4H); 7,58 (d, 2H); 7.40 (d, 1H); 7.30 (d, 1H); 7.28 (dt 2H); 7,23 (d:, 1H); 7.16 (d, 1H); 7,11 (d, 2H); 7.07 (d, 2H); 7.01 (df 2H); 6,90 (d, 2H); 3.81 (s, ΘΗ); 1.36 (s, 12H)
Step c: A mixture of 1,00 g (1.3 mmol) of stage b, 0.78 mL (3.9 mmol) of 5 molar NaOH and 15 mL of dioxane was degassed with argon for 30 min. Then 28 mg (0.05 mmol) of Pd[P(iBu)3]2 and 0.59 g (1.5 mmol) of the compound
were added, and the mixture was heated to 85*C and stirred tor 1 day. After cooling, the reaction mixture was added to ice-water and extracted with dichlonomethane. The solvent was removed from the organic phase. The residue was purified twice by means of column chromatography with the eluent 4:1 dicM>rom©thane:methanol, This gave 630 mg of a red solid, which corresponds to a yield of 88%.
Analytical data: >H NMR (500MHz, DMSO, 25’C): 5 - 8.75 (d, 1H); 8,58 (d, 1Hfc 8,51 (d, IN); 7.98 (m, 2H); 7.65 (d, 4H); 7,82 (d, 2H); 7.53 (sf 2H); 7,45 {a, 2H); 7,26 (d, 2H); 7.11 (d, 2H); 7.07 (d, 2H); 7.02 (d, 2H); 6.90 {d, 2H); 4,.51 (e, 2H); 3.81 (s, 6H); 1,36 (s, 12H)
Example 4: -x
The preparation proceeds from 4-hfixyioxybromobenzene, which was reacted with p-hexyloxybrcmobenzene {step a). “Hie resulting amine was reacted further with 1,4-dlbromobenzene (step b). This was followed by coupling with 2t2-bisthiophene-5-boronlc ester (step c) and bromlnation (step d). Finally, coupling was effected with 2-boronic ester naphtha Mde and the ester group was deproteeied (step e).
Step a: A mixture of 2.0 g (78 mmol] of 4-haxyioxybiomobenzene, 18 g {93 mmol) of p-hexyloxybromobenzene, 0.87 g (3:9 mmol) of palladlum(H) acetate, 3,1 g {5.8 mmol) of DPEphos, 12 g (125 mmoi) of sodium tert-butoxlde and 100 mL of toluene was heated to 1Q0"C and stirred for one day. After cooing, the solvent was removed from the reaction mixture.. The crude product was purified by means of column chromatography with the eluent 2:1 dichloromethane:hexane, 19.7 g of a white solid were obtained, which corresponds to a yield of 88%.
Analytical data.: m nm <500 MHz, 00202,25°C}: 6 ~ 8.91 (d:, 4H): 8.79 (d, 4H); 5.35 (s, 1H>; 3.90 (t, 4H); 1.74 (m, 4H); 1.45 (m, 4H); 134 (m, 8H}; 0.91
Step b: A mixture of 5.4 g {14.6 mmol} of stage a, 6.9 g (29.2 mmoi) of 1,4-dibramobenzene, 275 mg (0.30 mmol) of Pds{dbah, 405 mg (0.73 mmol) of DPPF, 2.80 g (29.2 mmol) of sodium tart-butoxide and 40 mL of toluene was heated to 9Q6C and stirred for 2 days. After cooling, the solvent was removed from the reaction mixture. The purification was effected by means of column chromatography with the eluent 4:1 hexane:dicbloromethane. 5.6 g of a light-colored oil were obtained, which corresponds to a yield of 72%.
Analytical data: <H NMR (500MHz, DM SO, 25%'): 5« 7.29 (d, 2H); 6.99 (d, 4H); 6.89 (d, 4H); 6.66 (d, 2H); 3.92. (t, 4H); 1.89 (m, 4H); 1.40 (m, 4H); 1,30 (m, 8H); 0.88 (1, 6H)
Step c: A mixture of 1,6 g of stage b (3,1 mmoi), 15 mL of dioxane and 1,88 ml (9.3 mmol) of 5 molar NaQH was degassed with argon for 30 min. Then 51 mg (0.,11 mmoi) of Pd[P(tSu)3js and 0.98 g ¢3,31 mmol) of 2,2*bisthiophene-S4»ronic ester were added, and the mixture was heated to 85*C and stirred over the weekend. After cooling, the reaction mixture was added to ice-wafer and extracted with dichicromethane. The solvent was removed from the organic phase. The purification was effected by means of column chromatography with the eluent n-hexane + 2% ethyl acetate. This gave 1.62 g of a yellow solid, which corresponds to a yield of 88%.
Analytical data: Ή NMR {300MHz, DMSO, 25"C); 0 = 7.48 (m, 3H); 7.30 (m. 2H); 725 (d, 1H); 7,09 (q, 1H); 7.03 (q, 4H); 6.92 (q, 4H); 6.76 (q, 2H); 3.94 (t, 4H); 1.70 (m, 4H); 1,41 (m, 4H); 1.31 (m, 8H); 0.83 (t, SH)
Step d A solution of 430 mg (2,40 mmol) of N-bromosucarnkte and 10 ml of DMF was added dropwise at 0-5*0 to a mixture of 1.2 g (2.00 mmol) of stage c and 30 ml of DMF. Stirring was then continued at this temperature for 15 min and then 10 ml. of dilute sodium thiosulfate solution were added. The reaction mixture was added to 150 ml of demineralized water and extracted with MTBE, and tie solvent was removed from the organic phase. 1.0 g of a yellow sold was obtained, which corresponds to a yield of 73%,
Anaiytical data: rH NMR (500MHz, DMSO, 2B*C): 8 = 7.46 (d, 2H>; 7.29 (d, 1H); 7,27 {d, 1H); 7.21 (df 1H); 7,14 (d, 1H); 7.03 (d, 4H); 6.92 (d, 4H); 8.75 (d, 2H); 3.94 (t, 4H); 1.70 (m, 4H); 1.41 (m, 4H); 1,31 (m, SH); 0.98 {t, 8H)
Step e: A mixture of 0.,90 g (1,3 mmol) of stage d, 0.78 ml (3.9 mmol) of 5 rrtoldr NaQH and 15 mL of dioxane was degassed with argon for 30 min. Then 22 mg (0.04 mmol) of Pd[P(t8u)3]s and 0,91 g (1.5 mmol) of the compound
were added, and the mixture was heated to SS^C and stirred for 1 day. After cooling, the reaction mixture was added to ice-water and extracted with diehioromethane* and the solvent was removed from the organic phase. The residue was purified twice by means of column chromatography with the eluent 4:1 dldiloromethanemiethanol + 1% triethylamlne. Protected target product was obtained, which was stirred with 1:1 THFrwater and 1 g of KGH at 65*0 overnight. After cooling, the reaction mixture was added to water end 1 δ ml of cone, HCf were added The mixture was stirred at room temperature for 1 h. Then the mixture was extracted with dichicrom ethane and the solvent was then removed from the organic phase* The crude product was purified by means of column chromatography with the eluent 4:1 dichbromethane:methanol + 2% tnethylanriine, This gave 610 mg of a red solid* which corresponds to a yield of 54%.
Analytical data: Ή NMR (500MHz, DMSQ, 25X): 5-8.78 (d, IN); 8.60 (d, 1H); 8.53 (d, 1H); 7.97 (m, 2H); 7.53 (m, 4H); 7.41 (d, 1H); 7.34 (d, 1H); 7.03 {d, 4H>; 6.92 (d, 4H); 6.77 (d, 2H); 4.72 (s, 2H); 3.93 ft 4H}; 1.70 (m, 4H>; 1.41 (m, 4H); 131 (m, SH); 0.88 ft 6h)
Example 5 (compound occurred as a mixture of the isomers 5a and Sh}:
[4.(5’·- Bromo-f2.2) bssth iophenyS-5-yi)phenyl]bts(9,9-di meth>19H-8uoren-2-yl)amine (450 mg , 0.62 mmol) was dissolved in dioxane (15 ml), 5 molar NaOH (0.4 ml, 1.9 mmol) was added and the mixture was degassed with argon, for 30 min. Then Pd[P{tBu)s]2 (10 mg, 0.02 mmol) and 0--(4,4.5,5-tetraimethyl~[1 ,3,2jdioxahQralan-2-yi}benzQ[de]isoehromene“1 ,3-dfone (330 mg, 1 mmol) were introduced and the mixture was stirred at 85*C overnight. After cooling, the mixture was added to ice-water and extracted with diehiorom ethane, and the organic phase was concentrated. This gave 490 mg of an orange solid.
Maldi-foS; M+ - 837,27 8-(544-18 MS, 9-ctt methyl“9H“fluoren~2"y1)amj no] phen y!I2 t2f]bi th iopherty l'5-y E}-bonzo[d:©]!socEiromene-1,3-dfOne (400 mg, 0.48 mmol), zinc acetate <88 mg, 0.22 mmol) and 3,4-diaminobenzosc acid (220 mg. 144 mmol} were introduced into quinoline (40 ml). The mixture was heated: to 220“0 and stirred for 7 h. After cooling, precipitation was effected with 6% HCE, and the solid was filtered oft with suction and washed with hot water and a little ethanol. Column chromatography with 5:1 dichloromethane:methanol gave 98 mg (21%) of an orange solid.
Matdi-MS: M+ = 953.24
Use Examples:
The substrates used were glass plates which had been coated with fluorine-doped tin oxide (FTO) and had dimensions of 25 mm x 15 mm x 3 mm (Nippon Sheet Glass), which had been treated successively with glass cleaner (RBS 35). demineralized water and acetone, in each case tor 5 min In an ultrasound bath, then boiled in isopropanol for 10 minutes and dried in a nitrogen stream.
To produce the solid TiQa barrier layer, a spray pyrolysis process as described in Peng et ai,, Coord. Cham, Rev. 248 ¢2004), 1479, was used. The TiCfe paste DSL 18NR-T (Dyesol) was printed onto the solid TiCfe barrier layer In a screenprinting process. The paste consisted of TfQa particles with a diameter of approx, 26 nm. which were dispersed in a terpineoi/ethyiceilulose mixture, After the printing process, the paste was dried at 80*C for 5 minutes. This was followed by sintering at 45tFG for 30 minutes. The resulting uanoporous TO? layer had a. layer thickness of 1.8 pm.
For electrical Ensu Elation between metal back electrodes and working electrodes, as well as the ΉΟ2 layer, strips of poiylmide (PyroJin Pdyimide Coating, Supelco) were placed along each longitudinal side and cured in a drying cabinet at 200*0 for 15 min,
After removal from the drying cabinet, the sample was cooled to 8QeC, immersed into a5x 1CH molar ethanofic solution of hydimamic acid salt (the salt was obtained by reacting the commercially available hydrcxamic add with sodium hydroxide solution)
for 18 h, then removed, washed briefly with EtOH and then placed into a 5 x 10* molar solution of the inventive dye or a solution of the comparative compound JK2 in dtohloromethane for 1 h.
The sample removed from ihe solution was subsequently rinsed with pure advent (here dfchlororrseihane) and dried in a nitrogen stream. A p-conductor solution was spun onto the dried sample. The solution consisted of: 0.16 M spire-MeOTAD (Merck) in chlorobenzene and 0.3 M UNCSOsCFafe (Aldrich) in cyclohexanone in a ratio of 15:1 end 2.5 percent by weight of V2O5 based on spiro-MeOTAD. 125 pj of this solution were applied to the sample and allowed to act. for 60 s. Thereafter, the excess solution was spun off at 2000 rpm for 30 s,
The metal back electrode was applied by thermal metal vaporization under reduced pressure.
For this purpose, the sample was provided with a mask, in order to apply 8 separate back electrodes with dimensions of 0,13 cm3 to the active region, For this purpose, Ag was vaporized at a rate 3.0-3.5 nm/s at a pressure of approx, 5*10-« mbar, so· as to result in a layer thickness of 200 nm.
The quantum efficiency (IPCE ~ Incident Photon-to-ourrent Conversion Efficiency) was measured with a 75 waft xenon arc lamp (LOT-Oriel}, a 1(8 m monochromator (SpectraPro-21 SOI; Acton Research Corporation), a tnaneimpedance amplifier (Aescusoft GmbH Automation) and a lock-in amplifier 7265 (Signal Recovery),
Gurrent/voitage characteristics were obtained at an illumination intensity of 100 mWtem* {xenon tamp (LQT-Qriel) with AM1.5 filter) by varying the voltage between -0,8 V and +1.0 V and measuring the resulting short circuit current The data for different inventive compounds and the prior art compound JK2 are shown in Table 1 (Isc: short circuit current, Vbc- open circuit voltage; FF: fill factor; ETA: efficiency).
Table I
*: *3a (toiuene)”jneans that the dye was not applied as usual from dichtaromefhane solution, but from toluene solution.
Figure 1 shows the EQE values of the inventive compounds and of the prior art compound JK2 as a function of wavelength.
Figure 2 shows a comparison of the lightfastness of the inventive dye of compound 2a compared to the prior art dye JK2, in each case on T1O2. The irradiation series was commenced after 2 h of "light soaking" in the sun tester.
Figure 3 shows the efficiency of a short-circuited solar cell with dye 2a as a function of time. To determine the efficiency, the current/voltage characteristic was recorded in a Source Meter Model 2400 (Keithley Instruments Inc.) with irradiation using a power of 100 mW/cm2 (xenon lamp (LOT-Oriel) with AM1.5 filter).
It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.
In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word “comprise” or variations such as “comprises” or “comprising” is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.

Claims (5)

  1. Claims
    1. A compound of the forumula la, lb or l*b
    in which R are identical or different aryloxy, arylthio, hetaryloxy or hetarylthio radicals, n is 0, 1, 2, 3, 4 or 5, B is Ci-C6-alkylene or 1,4-phenylene, where the phenylene radical may be mono- or polysubstituted by alkyl, nitro, cyano and/or halogen, A is -COOM, -SO3M or -PO3M, M is hydrogen, an alkali metal cation or [NR'4]+, R' is hydrogen or alkyl, where the R' radicals may be the same or different, L is a bridge of the formula
    which may be mono- or polysubstituted by phenyl, alkyl, alkoxy, alkylthio and/or -NR4R5, and in which Ar is aryl or hetaryl which may be fused to saturated or unsaturated 5- to 18-membered rings which may comprise heteroatoms which may be the same or different in the case of two or three Ar, R4, R5 are each independently hydrogen, alkyl whose carbon chain may be interrupted by one or more -Ο-, -S-, -CO-, -SO- and/or -SO2- moieties, aryl or hetaryl, each of which may be mono- or polysubstituted by alkyl, alkoxy and/or alkylthio, R1, R2 are each independently radicals of the formula lla or Mb
    (Ma) (Mb) R3 is phenyl, alkyl, alkoxy, alkylthio or -NR7R8, m is 0, 1, 2, 3 or 4, X is C(R6R7)2, NR8, oxygen or sulfur and R6, R7, R8 are each independently hydrogen, alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -S02- moieties, aryl or hetaryl, each of which may be mono- or polysubstituted by alkyl, alkoxy and/or alkylthio.
  2. 2. A compound according to claim 1, wherein, in the formulae la, lb and l*b, R are identical or different aryloxy or arylthio radicals, n is 0, 1 or 2, B is Ci-C6-alkylene, A is-COOM, M is hydrogen or an alkali metal cation, L is a bridge of the formula
    which may be mono- or polysubstituted by phenyl, Ci-Ci2-alkyl, Ci-Ci2-alkoxy, Ci-Ci2-alkylthio and/or -NR4R5, and in which Ar is identical or different aryl or hetaryl which may be fused to saturated or unsaturated 5- to 18-membered rings which may comprise heteroatoms, R4, R5 are each independently hydrogen, Ci-Ci2-alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -C0-, -SO- and/or -SO2- moieties, R1, R2 are each independently radicals of the formulae ll'a and ll'b
    (I la) (ll'b) R3 is CrCi2-alkoxy, m is 0 or 1, X is C(R6R7)2, NR8, oxygen or sulfur and R6, R7, R8 are each independently hydrogen, Ci-Ci2-alkyl whose carbon chain may be interrupted by one or more -0-, -S-, -CO-, -SO- and/or -SO2- moieties.
  3. 3. A compound according to claim 1, wherein, in the formulae la, lb and l*b, n is 0, B is Ci-C6-alkylene, A is-COOM, M is hydrogen or an alkali metal cation, L is a bridge of the formula
    in which Ar is identical or different aryl or hetaryl, R1, R2 are each independently radicals of the formulae ll'a and ll'b
    (ll'a) (M'b) R3 is Ci-Ci2-alkoxy, m is 0 or 1, X is C(R6R7)2 and R6, R7 are each independently hydrogen or Ci-Ci2-alkyl.
  4. 4. The use of a compound of the formula la, lb or l*b or mixtures of compounds of the formulae la, lb and l*b according to claim 1,2 or 3 as photosensitizers in solar cells and photodetectors.
  5. 5. A solar cell or photodetector comprising a compound of the formula la, lb or l*b or mixtures of compounds of the formulae la, lb and l*b according to claim 1,2 or 3 photosensitizers.
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