US20170178823A1 - Boron containing perylene monoimides, a process for their production, their use as building blocks for the production of perylene monoimide derivatives, monoimide derivatives and their use in dye-sensitized solar cells - Google Patents
Boron containing perylene monoimides, a process for their production, their use as building blocks for the production of perylene monoimide derivatives, monoimide derivatives and their use in dye-sensitized solar cells Download PDFInfo
- Publication number
- US20170178823A1 US20170178823A1 US15/451,946 US201715451946A US2017178823A1 US 20170178823 A1 US20170178823 A1 US 20170178823A1 US 201715451946 A US201715451946 A US 201715451946A US 2017178823 A1 US2017178823 A1 US 2017178823A1
- Authority
- US
- United States
- Prior art keywords
- alkyl
- general formula
- hydrogen
- aryl
- perylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 31
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 title abstract description 13
- 238000004519 manufacturing process Methods 0.000 title description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title description 3
- 229910052796 boron Inorganic materials 0.000 title description 3
- -1 radicals hydrogen Chemical class 0.000 claims description 564
- 150000001875 compounds Chemical class 0.000 claims description 90
- 125000000217 alkyl group Chemical group 0.000 claims description 83
- 229910052739 hydrogen Inorganic materials 0.000 claims description 83
- 239000001257 hydrogen Substances 0.000 claims description 81
- 125000003118 aryl group Chemical group 0.000 claims description 74
- 125000001072 heteroaryl group Chemical group 0.000 claims description 53
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 41
- 150000002431 hydrogen Chemical class 0.000 claims description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 229910052760 oxygen Inorganic materials 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 31
- 125000003545 alkoxy group Chemical group 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 25
- 125000004104 aryloxy group Chemical group 0.000 claims description 20
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 19
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 18
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 18
- 125000004986 diarylamino group Chemical group 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 18
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 16
- 125000001424 substituent group Chemical group 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 14
- 125000005110 aryl thio group Chemical group 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 125000004414 alkyl thio group Chemical group 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 229910052727 yttrium Inorganic materials 0.000 claims description 11
- PXACTUVBBMDKRW-UHFFFAOYSA-M 4-bromobenzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=C(Br)C=C1 PXACTUVBBMDKRW-UHFFFAOYSA-M 0.000 claims description 7
- SPXOTSHWBDUUMT-UHFFFAOYSA-M 4-nitrobenzenesulfonate Chemical compound [O-][N+](=O)C1=CC=C(S([O-])(=O)=O)C=C1 SPXOTSHWBDUUMT-UHFFFAOYSA-M 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- SYGWYBOJXOGMRU-UHFFFAOYSA-N chembl233051 Chemical compound C1=CC=C2C3=CC(C(N(CCN(C)C)C4=O)=O)=C5C4=CC=CC5=C3SC2=C1 SYGWYBOJXOGMRU-UHFFFAOYSA-N 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 80
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 25
- 239000007787 solid Substances 0.000 description 24
- 0 CC.CC.[1*]C1=CC2=C3C(=C1)/C=C\C=C3\C1=C\C=C3\C(=O)[Y]C(=O)C4=C3C1=C2C=C4 Chemical compound CC.CC.[1*]C1=CC2=C3C(=C1)/C=C\C=C3\C1=C\C=C3\C(=O)[Y]C(=O)C4=C3C1=C2C=C4 0.000 description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 150000003254 radicals Chemical class 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000011541 reaction mixture Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(II) bromide Substances [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 10
- 239000012442 inert solvent Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 8
- YCVYMOGTZWOSHL-UHFFFAOYSA-N CC.CC.CC1=CC2=C3C(=C1)/C=C\C=C3\C1=C\C=C3\C(=O)[Y]C(=O)C4=C3C1=C2C=C4 Chemical compound CC.CC.CC1=CC2=C3C(=C1)/C=C\C=C3\C1=C\C=C3\C(=O)[Y]C(=O)C4=C3C1=C2C=C4 YCVYMOGTZWOSHL-UHFFFAOYSA-N 0.000 description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- PSYJKHYMCITPES-UHFFFAOYSA-N C1=CC2=C(C=C1)C1=C(/C=C\C=C/1)C2.C1=CC=CC=C1.CC.CC.CC.CC Chemical compound C1=CC2=C(C=C1)C1=C(/C=C\C=C/1)C2.C1=CC=CC=C1.CC.CC.CC.CC PSYJKHYMCITPES-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 125000006617 triphenylamine group Chemical group 0.000 description 7
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 239000002798 polar solvent Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000003107 substituted aryl group Chemical group 0.000 description 6
- MNKCGUKVRJZKEQ-MIXQCLKLSA-N (1z,5z)-cycloocta-1,5-diene;iridium;methanol Chemical compound [Ir].[Ir].OC.OC.C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 MNKCGUKVRJZKEQ-MIXQCLKLSA-N 0.000 description 5
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical group CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 description 5
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- MLWSVGKPFFPXIS-UHFFFAOYSA-N C1=CC(C(C)(C)CC(C)(C)C)=CC=C1N(C=1C=C2C=3C=CC4=C5C(C(N(CC(O)=O)C4=O)=O)=CC=C(C=35)C=3C=CC(=C(C2=3)C=1)N(C=1C=CC(=CC=1)C(C)(C)CC(C)(C)C)C=1C=CC(=CC=1)C(C)(C)CC(C)(C)C)C1=CC=C(C(C)(C)CC(C)(C)C)C=C1 Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1N(C=1C=C2C=3C=CC4=C5C(C(N(CC(O)=O)C4=O)=O)=CC=C(C=35)C=3C=CC(=C(C2=3)C=1)N(C=1C=CC(=CC=1)C(C)(C)CC(C)(C)C)C=1C=CC(=CC=1)C(C)(C)CC(C)(C)C)C1=CC=C(C(C)(C)CC(C)(C)C)C=C1 MLWSVGKPFFPXIS-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000003282 alkyl amino group Chemical group 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 3
- GSWCRDNWOZAAIK-UHFFFAOYSA-N 4-(pentan-3-ylcarbamoyl)-8,11-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)perylene-3-carboxylic acid Chemical compound C=1C(=C23)C(C4=5)=CC=C(C(O)=O)C=5C(C(O)=NC(CC)CC)=CC=C4C2=CC(B2OC(C)(C)C(C)(C)O2)=CC3=CC=1B1OC(C)(C)C(C)(C)O1 GSWCRDNWOZAAIK-UHFFFAOYSA-N 0.000 description 3
- AQNVYZBKNTUQKS-UHFFFAOYSA-N C1=CC(C2=CC(N(C=3C=C4C(C)(C)C5=CC=CC=C5C4=CC=3)C3=CC=C4C5=CC=CC=C5C(C4=C3)(C)C)=CC=3C2=C2C=CC=3)=C3C2=CC=C2C(=O)N(CC(O)=O)C(=O)C1=C32 Chemical compound C1=CC(C2=CC(N(C=3C=C4C(C)(C)C5=CC=CC=C5C4=CC=3)C3=CC=C4C5=CC=CC=C5C(C4=C3)(C)C)=CC=3C2=C2C=CC=3)=C3C2=CC=C2C(=O)N(CC(O)=O)C(=O)C1=C32 AQNVYZBKNTUQKS-UHFFFAOYSA-N 0.000 description 3
- MJVPREHTEYJKBS-UHFFFAOYSA-N C1=CC=C2C(C)(C)C3=CC(N(C=4C=C5C(C)(C)C6=CC=CC=C6C5=CC=4)C=4C=C5C6=CC=C7C(=O)N(C(C8=CC=C(C6=C78)C=6C=C(C=C(C5=6)C=4)N(C=4C=C5C(C)(C)C6=CC=CC=C6C5=CC=4)C=4C=C5C(C)(C)C6=CC=CC=C6C5=CC=4)=O)C(CC)CC)=CC=C3C2=C1 Chemical compound C1=CC=C2C(C)(C)C3=CC(N(C=4C=C5C(C)(C)C6=CC=CC=C6C5=CC=4)C=4C=C5C6=CC=C7C(=O)N(C(C8=CC=C(C6=C78)C=6C=C(C=C(C5=6)C=4)N(C=4C=C5C(C)(C)C6=CC=CC=C6C5=CC=4)C=4C=C5C(C)(C)C6=CC=CC=C6C5=CC=4)=O)C(CC)CC)=CC=C3C2=C1 MJVPREHTEYJKBS-UHFFFAOYSA-N 0.000 description 3
- MGDYFEURMLLQKI-UHFFFAOYSA-N C1=CC=C2C(C)(C)C3=CC(N(C=4C=C5C(C)(C)C6=CC=CC=C6C5=CC=4)C=4C=C5C=C(C=C6C=7C=CC8=C9C(C(N(CC(O)=O)C8=O)=O)=CC=C(C=79)C(=C56)C=4)N(C=4C=C5C(C)(C)C6=CC=CC=C6C5=CC=4)C4=CC=C5C6=CC=CC=C6C(C5=C4)(C)C)=CC=C3C2=C1 Chemical compound C1=CC=C2C(C)(C)C3=CC(N(C=4C=C5C(C)(C)C6=CC=CC=C6C5=CC=4)C=4C=C5C=C(C=C6C=7C=CC8=C9C(C(N(CC(O)=O)C8=O)=O)=CC=C(C=79)C(=C56)C=4)N(C=4C=C5C(C)(C)C6=CC=CC=C6C5=CC=4)C4=CC=C5C6=CC=CC=C6C(C5=C4)(C)C)=CC=C3C2=C1 MGDYFEURMLLQKI-UHFFFAOYSA-N 0.000 description 3
- UPCYLWWAHBNECF-UHFFFAOYSA-N C1=CC=C2C(C)(C)C3=CC(N(C=4C=C5C(C)(C)C6=CC=CC=C6C5=CC=4)C=4C=C5C=CC=C6C7=CC=C8C(=O)N(C(C9=CC=C(C7=C89)C(C=4)=C65)=O)C(CC)CC)=CC=C3C2=C1 Chemical compound C1=CC=C2C(C)(C)C3=CC(N(C=4C=C5C(C)(C)C6=CC=CC=C6C5=CC=4)C=4C=C5C=CC=C6C7=CC=C8C(=O)N(C(C9=CC=C(C7=C89)C(C=4)=C65)=O)C(CC)CC)=CC=C3C2=C1 UPCYLWWAHBNECF-UHFFFAOYSA-N 0.000 description 3
- FPRNVVZTWOXVEJ-UHFFFAOYSA-N CB(O)O.[W] Chemical compound CB(O)O.[W] FPRNVVZTWOXVEJ-UHFFFAOYSA-N 0.000 description 3
- UODSSOIAWCCNHV-UHFFFAOYSA-N CC.O=C1[Y]C(=O)/C2=C/C=C3\C4=C(C=CC1=C42)C1=C2C(=CC=C1)/C=C\C=C\23 Chemical compound CC.O=C1[Y]C(=O)/C2=C/C=C3\C4=C(C=CC1=C42)C1=C2C(=CC=C1)/C=C\C=C\23 UODSSOIAWCCNHV-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- 229920006934 PMI Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- IBWAVZDUXUXUAJ-UHFFFAOYSA-N 12-[4-(2,4,4-trimethylpentan-2-yl)-N-[4-(2,4,4-trimethylpentan-2-yl)phenyl]anilino]-16-azahexacyclo[12.6.2.12,6.011,21.018,22.010,23]tricosa-1(21),2,4,6(23),7,9,11,13,18(22),19-decaene-15,17-dione Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1N(C=1C=2C=3C=CC=C4C=CC=C(C=34)C3=CC=C4C(C=23)=C(C(NC4=O)=O)C=1)C1=CC=C(C(C)(C)CC(C)(C)C)C=C1 IBWAVZDUXUXUAJ-UHFFFAOYSA-N 0.000 description 2
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- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- PQPFFKCJENSZKL-UHFFFAOYSA-N pentan-3-amine Chemical compound CCC(N)CC PQPFFKCJENSZKL-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002979 perylenes Chemical class 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- 231100000289 photo-effect Toxicity 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 125000004424 polypyridyl Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 description 1
- 125000004353 pyrazol-1-yl group Chemical group [H]C1=NN(*)C([H])=C1[H] 0.000 description 1
- 125000004289 pyrazol-3-yl group Chemical group [H]N1N=C(*)C([H])=C1[H] 0.000 description 1
- 125000004497 pyrazol-5-yl group Chemical group N1N=CC=C1* 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002206 pyridazin-3-yl group Chemical group [H]C1=C([H])C([H])=C(*)N=N1 0.000 description 1
- 125000004940 pyridazin-4-yl group Chemical group N1=NC=C(C=C1)* 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000004527 pyrimidin-4-yl group Chemical group N1=CN=C(C=C1)* 0.000 description 1
- 125000004528 pyrimidin-5-yl group Chemical group N1=CN=CC(=C1)* 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- CMJDSHGPZPMYQN-UHFFFAOYSA-N sodium;2-(4-butoxyphenyl)-n-oxidoacetamide Chemical compound [Na+].CCCCOC1=CC=C(CC(=O)N[O-])C=C1 CMJDSHGPZPMYQN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/18—Ring systems of four or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H01L51/0053—
-
- H01L51/0061—
-
- H01L51/008—
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/658—Organoboranes
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- H01L51/0058—
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/10—Photovoltaic [PV]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates
- the direct conversion of solar energy to electrical energy in solar cells is based on the internal photoeffect of a semiconductor material, i.e. the generation of electron-hole pairs by absorption of photons and the separation of the negative and positive charge carriers at a p-n junction or a Schottky contact.
- the photovoltage thus generated can bring about a photocurrent in an external circuit, through which the solar cell delivers its power.
- Thin layers or films of metal oxides are known to constitute inexpensive solid semiconductor materials (n-semiconductors), but their absorption, owing to large band gaps, is typically not within the visible region of the electromagnetic spectrum.
- the metal oxides therefore have to be combined with a photosensitizer which absorbs in the wavelength range of sunlight, i.e. at from 300 to 2000 nm, 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 cell and is reduced at the counterelectrode, electrons are recycled to the sensitizer which is thus regenerated.
- DSCs Dye-sensitized solar cells which are based on titanium dioxide as the semiconductor material are described, for example, in U.S. Pat. No. 4,927,721, Nature 353, p. 737-740 (1991) and U.S. Pat. No. 5,350,644, and also Nature 395, p. 583-585 (1998) and EP-A-1 176 646.
- These solar cells comprise monomolecular films of transition metal complexes, especially ruthenium complexes, which are bonded to the titanium dioxide layer via acid groups, as sensitizers and iodine/iodide redox systems present in dissolved form or amorphous organic p-conductors based on spirobifluorenes.
- metal-free organic dyes have attracted increasing attention as they do not contain any toxic or costly metal and their properties are easily tuned by facile structural modification.
- they generally have much higher extinction coefficients when compared to Ru(II) polypyridyls, making them excellent for use in solid state DSCs in combination with hole transporting materials such as P3HT as shown, for example, by G. K. Mor, S. Kim, M. Paulose, O. K. Varghese, K. Shankar, J. Basham and C. A. Grimes, Nano Lett., 2009, 9, 4250, or spiro-MeOTAD as shown, for example, by H. J. Snaith, A. J. Moule, C. Klein, K. Meerholz, R. H. Friend, M. G ⁇ umlaut over (r) ⁇ atzel, Nano Lett., 2007, 7, 3372.
- perylene-3,4:9,10-tetracarboxylic acid derivatives as sensitizers are examined in Japanese documents JP-A-10-189065, 2000-243463, 2001-093589, 2000-100484 and 10-334954, and in New J. Chem. 26, p. 1155-1160 (2002).
- the main object of the present invention to provide further convenient building blocks for the preparation of 8- and/or 11-substituted PMIs and 8- and/or 11-substituted PMIs per se for the application in DSCs which exhibit good to very good quantum efficiencies and very good medium to long term stabilities.
- Preferred compounds of general formula I are those wherein the variables have the following meaning
- a further objective of the instant invention is a process for the preparation of compounds of general formula I which comprises
- a preferred process for the preparation of compounds of general formula I according to the instant invention comprises
- a specifically preferred process for the preparation of compounds of general formula I according to the instant invention comprises
- ambient pressure denotes basically unconfined reaction conditions, however, not excluding the application of protective gas atmosphere in order to avoid adverse effects by oxygen/air and/or moisture.
- “Inert solvent” means a solvent which does not contain moieties with either basic or acidic properties. Especially groups with acidic hydrogen atoms must not be present. In the case of a aromatic or heteroaromatic solvent this may only contain less than three neighboring hydrogen atoms directly bound to the carbon atoms or heteroatoms of the aromatic or heteroaromatic solvent skeleton in order to prevent the aromatic or heteroaromtic solvent from reacting with the boron containing educt.
- inert solvent is meant to embrace mixtures of inert solvents as well.
- Suitable inert solvents are e.g. dimethyl formamide (DMF), tetrahydofuran (THF), 1,4-dioxan, octane, hexane, pentane, mesitylene, pinacolone etc. and mixtures thereof.
- a further objective of the instant invention is to provide a process for the preparation of compounds of general formula II
- confined conditions refers to reaction conditions in which the reactants during the reaction are placed in a tightly sealed reaction vessel, ampoule or the like.
- Polar solvent typically refers to a solvent which is readily miscible with water.
- polar solvent is meant to embrace mixtures of polar solvents as well. Suitable polar solvents are e.g. water, dimethyl formamide (DMF), tetrahydofuran (THF), 1,4-dioxan, short carbon chain alcohols like e.g. butanol, i-butanol, tert.-butanol, propanol, i-propanol, ethanol or methanol and mixtures thereof.
- DMF dimethyl formamide
- THF tetrahydofuran
- 1,4-dioxan 1,4-dioxan
- short carbon chain alcohols like e.g. butanol, i-butanol, tert.-butanol, propanol, i-propanol, ethanol or methanol and mixtures thereof.
- the leaving group Lg can be any group known to a person skilled in the art as being prone to easily leave the molecule.
- Lg consists of or comprises strongly electron-withdrawing atoms or moieties and, thus, is normally split off as anionic species.
- Preferred groups Lg are chlorine, bromine, iodine, brosylate, nosylate, tosylate, mesylate and triflate which, in view of the aforesaid, leave the molecule as chloride, bromide, iodide, brosylate, nosylate, tosylate, mesylate (“mes”—H 3 C—SO 3 ⁇ ) or triflate (“tri”—F 3 C—SO 3 ) anion.
- brosylate brosylate
- nosylate nosylate
- tosylate tosylate
- preferred reagents Cu(Lg) 2 are CuCl 2 , CuBr 2 , CuI 2 , Cu(bros) 2 , Cu(nos) 2 , Cu(tos) 2 , Cu(mes) 2 and Cu(tri) 2 .
- a further objective of the instant invention is a process for the preparation of compounds of general formula III
- the Buchwald-Hartwig amination reaction is a well established synthetic route and the reaction conditions can easily be determined by a person skilled in the art. Conversion of aryl bromides to arylamines is specifically addressed in the publication by Guram, A. S.; Rennels, R. A.; Buchwald, S. L. (1995), “A Simple Catalytic Method for the Conversion of Aryl Bromides to Arylamines”, Angewandte Chemie International Edition 34 (12): 1348-1350.
- a further objective of the instant invention are compounds of general formula III
- a further objective of the instant invention is a process for the preparation of compounds of general formula IV
- a further objective of the instant invention are compounds of general formula IV
- a further objective of the instant invention are compounds of general formula IV
- a further objective or the instant invention is the use of
- a further objective or the instant invention is a dye-sensitized solar cell comprising
- alkyl, aryl or heteroaryl represents unsubstituted or substituted alkyl, unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl.
- Alkyl comprises straight-chain or branched alkyl.
- Alkyl is preferably C 1 -C 30 -alkyl, especially C 1 -C 2 -alkyl and most preferably C 1 -C 12 -alkyl.
- alkyl groups are especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.
- branched alkyl groups can be represented by the following formula
- the R a radicals are preferably selected from C 1 - to C 12 -alkyl, especially C 1 - to C 8 -alkyl.
- Preferred branched alkyl radicals of the above formula are, for example:
- Alkyl also comprises alkyl radicals whose carbon chains may be interrupted by one or more nonadjacent groups selected from oxygen, sulfur, —CO—, —NR b —, —SO— and/or —SO 2 — where R b is preferably hydrogen, unsubstituted straight-chain or branched alkyl as described before or unsubstituted aryl as described below.
- Substituted alkyl groups may, depending on the length of the alkyl chain, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro.
- Aryl-substituted alkyl radicals have at least one unsubstituted or substituted aryl group, as defined below.
- the alkyl group of the aralkyl radical may bear at least one further substituent and/or be interrupted by one or more nonadjacent groups selected from oxygen, sulfur, —CO—, —NR b- , —SO— and/or —SO 2 — where R b is preferably hydrogen, unsubstituted straight-chain or branched alkyl as described before or unsubstituted aryl as described below.
- Arylalkyl is preferably phenyl-C 1 -C 10 -alkyl, more preferably phenyl-C 1 -C 4 -alkyl, for example benzyl, 1-phenethyl, 2-phenethyl, 1-phenprop-1-yl, 2-phenprop-1-yl, 3-phenprop-1-yl, 1-phenbut-1-yl, 2-phenbut-1-yl, 3-phenbut-1-yl, 4-phenbut-1-yl, 1-phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl, 4-phenbut-2-yl, 1-(phenmeth)eth-1-yl, 1-(phenmethyl)-1-(methyl)eth-1-yl or -(phenmethyl)-1-(methyl)prop-1-yl; preferably benzyl and 2-phenethyl.
- Halogen-substituted alkyl groups comprise a straight-chain or branched alkyl group in which at least one hydrogen atom or all hydrogen atoms are replaced by halogen.
- the halogen atoms are preferably selected from fluorine, chlorine and bromine, especially fluorine and chlorine.
- haloalkyl groups are especially chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropy
- unsubstituted and substituted alkyl radicals which may be interrupted by one or more nonadjacent groups selected from oxygen, sulfur, —NR b —, —CO—, —SO— and/or —SO 2 — are:
- cycloalkyl denotes a cycloaliphatic radical having preferably 3 to 10, more preferably 5 to 8, carbon atoms.
- cycloalkyl groups are especially cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
- Substituted cycloalkyl groups may, depending on the ring size, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro. In the case of substitution, the cycloalkyl groups preferably bear one or more, for example one, two, three, four or five, C 1 -C 6 -alkyl groups.
- substituted cycloalkyl groups are especially 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 2-, 3- and 4-propylcyclohexyl, 2-, 3- and 4-isopropylcyclohexyl, 2-, 3- and 4-butylcyclohexyl, 2-, 3- and 4-sec.-butylcyclohexyl, 2-, 3- and 4-tert-butylcyclohexyl, 2-, 3- and 4-methylcycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 2-, 3- and 4-propylcycloheptyl, 2-, 3- and 4-isopropylcycloheptyl, 2-, 3- and 4-butylcycloheptyl, 2-, 3- and 4-sec-butylcycloheptyl, 2-, 3- and 4-tert-butylcyclohept
- substituted and unsubstituted cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclo-pentyl, 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-methyl-cycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 3- and 4-propylcycloheptyl, 3- and 4-iso-propylcycloheptyl, 3- and 4-butylcycloheptyl, 3- and
- aryl comprises mono- or polycyclic aromatic hydrocarbon radicals and monocyclic aromatic hydrocarbon radicals which may be fused to one or more unfused or fused saturated or unsaturated carbocyclic or heterocyclic five or six membered rings.
- Aryl has preferably 6 to 14, more preferably 6 to 10, carbon atoms. Examples of aryl are especially phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl and pyrenyl, especially phenyl, naphthyl and fluorenyl.
- Substituted aryls may, depending on the number and size of their ring systems, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro.
- the alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl and hetaryl substituents on the aryl may in turn be unsubstituted or substituted.
- the substituents on the aryl are preferably selected from alkyl, alkoxy, haloalkyl, haloalkoxy, aryl, fluorine, chlorine, bromine, cyano and nitro.
- Substituted aryl is more preferably substituted phenyl which generally bears 1, 2, 3, 4 or 5, preferably 1, 2 or 3, substituents.
- Substituted aryl is preferably aryl substituted by at least one alkyl group (“alkaryl”).
- Alkaryl groups may, depending on the size of the aromatic ring system, have one or more (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more than 9) alkyl substituents.
- the alkyl substituents may be unsubstituted or substituted. In this regard, reference is made to the above statements regarding unsubstituted and substituted alkyl.
- the alkaryl groups have exclusively unsubstituted alkyl substituents.
- Alkaryl is preferably phenyl which bears 1, 2, 3, 4 or 5, preferably 1, 2 or 3, more preferably 1 or 2, alkyl substituents.
- Aryl which bears one or more radicals is, for example, 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3-
- unsubstituted or substituted aryl also apply to unsubstituted or substituted aryloxy and unsubstituted or substituted arylthio.
- aryloxy are phenoxy and naphthyloxy.
- hetaryl comprises heteroaromatic, mono- or polycyclic groups and monocyclic groups which may be fused to one or more unfused or fused saturated or unsaturated carbocyclic or heterocyclic five or six membered rings.
- ring carbon atoms these have 1, 2, 3, 4 or more than 4 of the ring heteroatoms.
- the heteroatoms are preferably selected from oxygen, nitrogen, selenium and sulfur.
- the hetaryl groups have preferably 5 to 18, e.g. 5, 6, 8, 9, 10, 11, 12, 13 or 14, ring atoms.
- Monocyclic hetaryl groups are preferably 5- or 6-membered hetaryl groups, such as 2-furyl (furan-2-yl), 3-furyl (furan-3-yl), 2-thienyl (thiophen-2-yl), 3-thienyl (thiophen-3-yl), selenophen-2-yl, selenophen-3-yl, 1H-pyrrol-2-yl, 1H-pyrrol-3-yl, pyrrol-1-yl, imidazol-2-yl, imidazol-1-yl, imidazol-4-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-o
- Polycyclic hetaryl has 2, 3, 4 or more than 4 fused rings.
- the fused-on rings may be aromatic, saturated or partly unsaturated.
- Examples of polycyclic hetaryl groups are quinolinyl, isoquinolinyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, benzoxazolyl, benzisoxazolyl, benzthiazolyl, benzoxadiazolyl; benzothiadiazolyl, benzoxazinyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, benzotriazinyl, benzoselenophenyl, thienothiophenyl, thienopyrimidyl, thiazolothiazolyl, dibenzopyrrolyl (carbazolyl), dibenzofuranyl, dibenzothiophen
- Substituted heteroaryls may, depending on the number and size of their ring systems, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro.
- Halogen substituents are preferably fluorine, chlorine or bromine.
- the substituents are preferably selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, hydroxyl, carboxyl, halogen and cyano.
- Halogen represents fluorine, chlorine, bromine or iodine, preferably chlorine and bromine.
- Alkali cation represents sodium, potassium, rubidium and cesium, preferably sodium and potassium.
- R′ in the tetraalkyl ammonium cation [NR′] 4+ typically refers to methyl or tert.-butyl.
- DSCs generally comprise the following elements: an electrically conductive layer (being part of or forming the working electrode or anode), a photosensitive layer generally comprising a semiconductive metal oxide and a photosensitive dye, a charge transfer layer and another electrically conductive layer (being part of or forming the counter electrode or cathode).
- N-(1-ethylpropyl)-2,5-bis[3,3-dimethylbutyl]perylene-3,4-dicarboxylic acid monoimide (0.100 g, 0.179 mmol), bis(pinacolato)diboron (0.100 g, 0.393 mmol), [Ir(OMe)cod] 2 (bis(1,5-cyclooctadiene)dimethoxydiiridium; 5.9 mg, 8.9 ⁇ mol) and dtbpy (4,4′-di-tert-butyl-2,2′-bipyridyl; 4.8 mg, 17.9 ⁇ mol) were mixed in an oven dried flask under argon atmosphere.
- N-(1-ethylpropyl) perylene-3,4-dicarboxylic acid monoimide (2.00 g, 5.11 mmol), bispinacolondiboronate (3.11 g, 12.26 mmol), [Ir(OMe)cod] 2 (0.169 g, 0.255 mmol) and dtbpy (0.137 g, 0.511 mmol) were mixed in an oven dried flask under argon atmosphere. Anhydrous tetrahydrofuran (THF; 80 ml) was added and the reaction heated for 18 hours at 60° C. The solvent was evaporated and the reaction mixture dissolved in dichloromethane, precipitated in methanol and filtered.
- THF tetrahydrofuran
- N-(1-heptyloctyl)-perylene-3,4-dicarboxylic acid monoimide (0.76 g, 1.42 mmol), bispinacolondiboronate (0.87 g, 3.43 mmol), [Ir(OMe)cod] 2 (0.047 g, 0.255 mol) and dtbpy (0.137 g, 0.511 mmol) were mixed in an oven dried flask under argon atmosphere. Anhydrous THF (80 ml) was added and the reaction heated for 18 hours at 60° C. the solvent was evaporated and the reaction mixture dissolved in dichloromethane, precipitated in methanol and filtered.
- N-(1-ethylpropyl)-8, 11-bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-y]-perylene-3,4-dicarboxylic acid monoimide (0.600 g, 0.933 mmol) was suspended in a mixture of dioxane (100 ml), methanol (10 ml) and water (10 ml) in a 210 mL pressure vial. Copper(II) bromide (2.08 g, 9.33 mmol) was added, the vessel sealed and heated up to 120° C. for 12 hours. The reaction mixture was poured into 200 mL of 1.0 M hydrochloric acid and filtered to obtain a red solid. The desired compound C4 was obtained after column chromatography (silica, toluene) and crystallization from toluene as an orange solid (yield 48%, 0.25 g, 0.48 mmol).
- the monobrominated compound (also according to general formula II of the present invention)
- N-(1-heptyloctyl)-8,11-bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-y]-perylene-3,4-dicarboxylic acid monoimide (1.00 g, 1.28 mmol) was suspended in a mixture of THF (90 ml), methanol (10 ml) and water (10 ml) in a 210 mL pressure vial. Copper(II) bromide (2.85 g, 12.8 mmol) was added, the vessel sealed and heated up to 120° C. for 12 hours. The reaction mixture was poured into 200 mL of 1.0 M hydrochloric acid and filtered to obtain a red solid. The desired compound C5 was obtained after column chromatography (silica, toluene) and obtained as a bright orange solid (yield 38%, 0.34 g, 0.49 mmol).
- N-(1-ethylpropyl)-8,11-bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-y]-perylene-3,4-dicarboxylic acid monoimide (0.600 g, 0.933 mmol) was suspended in a mixture of dioxane (100 ml), methanol (10 ml) and water (10 ml) in a 210 mL pressure vial. Copper(II) chloride (1.254 g, 9.33 mmol) was added, the vessel sealed and heated up to 120° C. for 12 hours. The reaction mixture was poured into 200 mL of 1.0 M hydrochloric acid and filtered to obtain a red solid. The desired compound C6 was obtained after column chromatography (silica, toluene) and crystallization from toluene as a dark orange solid (yield 54%, 0.23 g, 0.50 mmol).
- the monochlorinated compound (also according to general formula II of the present invention)
- IR spectrum (ATR) ⁇ max [cm ⁇ 1] 3034, 2953, 2874, 2691, 1652, 1593, 1566, 1500, 1457, 1349, 1268, 1246, 1197, 1085, 808, 751.
- Elemental analysis (C 55 H 62 N 2 O 2 ): calculated: 84.36%; C, 7.98%; H, 3.58%; N, % S. found: 84.25%; C, 7.62%; H, 3.75%; N, % S.
- IR spectrum (ATR) ⁇ max [cm ⁇ 1 ] 2954, 2873, 1692, 1654, 1593, 1564, 1507, 1461, 1351, 1254, 1085, 1015, 805, 752.
- Elemental analysis (C 80 H 95 N 3 O 4 ): calculated: 82.65%; C, 8.24%; H, 3.61%; N, % S found: 81.66%; C, 8.62%; H, 3.68%; N, % S.
- IR spectrum (ATR) ⁇ max [cm ⁇ 1 ] 2951, 2901, 2871, 1697, 1662, 1593, 1561, 1506, 1365, 1250, 1172, 1132, 1013, 821, 755.
- reaction mixture was purified via gel permeation chromatography to separate mono- and difunctionalised product with chloroform and via column chromatography with dichloromethane.
- IR spectrum (ATR) ⁇ max [cm ⁇ 1 ] 3040, 2956, 2924, 2860, 1693, 1656, 1590, 1486, 1448, 1368, 1298, 1249, 1135, 1080, 1015, 966, 824, 777, 755, 734.
- IR spectrum (ATR) ⁇ max [cm ⁇ 1 ] 3630, 3499, 3058, 2957, 2923, 2860, 1750, 1691, 1651, 1591, 1570, 1448, 1407, 1370, 1292, 1247, 1172, 1073, 1020, 970, 853, 799, 755, 736.
- N-(1-heptyloctyl)-8,11-bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-y]-perylene-3,4-dicarboxylic acid (0.070 g, 0.09 mmol) and 1-bromo-2-nitrobenzene (0.054 g, 0.27 mmol) were mixed together and dissolved in 15 mL toluene and 0.15 mL ethanol.
- Potassium carbonate 148 mg, 1.07 mmol was dissolved in 1.5 mL of water and added to the reaction mixture.
- UV-vis in CH 2 Cl 2 : ⁇ max ( ⁇ [M ⁇ 1 cm ⁇ 1 ]): 476 nm (3.81 ⁇ 10 4 M ⁇ 1 cm ⁇ 1 ), 501 nm (4.20 ⁇ 10 4 M ⁇ 1 cm ⁇ 1 ).
- a TiO 2 blocking layer was prepared on a fluorine-doped tin oxide (FTO)-covered glass substrate using spray pyrolysis (cf. B. Peng, G. Jungmann, C. Jager, D. Haarer, H. W. Schmidt, M. Thelakkat, Coord. Chem. Rev. 2004, 248, 1479).
- a TiO 2 paste (Dyesol), diluted with terpineol, was applied by screen printing, resulting in a film thickness of 1.7 ⁇ m. All films were then sintered for 45 min at 450° C., followed by treatment in a 40 mM aqueous solution of TiCl 4 at 60° C.
- the active area of the sDSC was defined by the size of these contacts (0.13 cm 2 ), and the cells were masked by an aperture of the same area for measurements.
- the current-voltage characteristics for all cells were measured with a Keithley 2400 under 1000 W/m 2 , AM 1.5G conditions (LOT ORIEL 450 W).
- the incident photon to current conversion efficiency's were obtained with an Acton Research Monochromator using additional white background light illumination.
- the samples were illuminated with monochromatic light from the quartz monochromator with deuterium lamp.
- the power of the incident light beam was (2-5). 10-8 W.
- the negative voltage of ⁇ 300 V was supplied to the sample substrate.
- the counter-electrode with the 4.5 ⁇ 15 mm 2 slit for illumination was placed at 8 mm distance from the sample surface.
- the counter-electrode was connected to the input of the BK2-16 type electrometer, working in the open input regime, for the photocurrent measurement.
- the 10 ⁇ 15 -10 ⁇ 12 A strong photocurrent was flowing in the circuit under illumination.
- the photocurrent J is strongly dependent on the incident light photon energy h ⁇ .
Abstract
Boron-comprising perylene monoimides and a process for producing the boron-comprising perylene monoimides are provided. The boron-comprising perylene monoimides are useful as building blocks for producing perylene monoimide derivatives and monoimide derivatives. The boron-comprising perylene monoimides are also useful for preparing dye-sensitized solar cells.
Description
- Boron containing perylene monoimides, a process for their production, their use as building blocks for the production of perylene monoimide derivatives, monoimide derivatives and their use in dye-sensitized solar cells
- The present invention relates
- to compounds of general formula I
- wherein the variables have the following meaning
- E1, E2 a moiety of formula Ia
- m 0 or 1, where in the case of m equal 1 E2 is bound either to the 8 or 9 position of the perylene skeleton and is identical to E1,
- W a bridging C2 or C3 moiety which may be substituted by one or more alkyl,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- and
- R12 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM, —SO3M or —PO3M,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different, and
- Z C1-C6-alkylene or 1,4-phenylene, where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen,
and a process for the preparation of compounds of general formula I;
to a process for the preparation of compounds of general formula II
- wherein the variables have the following meaning
- Lg leaving group,
- m 0 or 1, where in the case of m equal 1 the one Lg is bound either to the 8 or 9 position of the perylene skeleton and is identical to the Lg bound to the 11 position,
and the remaining variables R3, n and Y have the abovementioned meaning, and to compounds of general formula II per se;
to a process for the preparation of compounds of general formula III - wherein the variables have the following meaning
- R1, R2 independently of each other a moiety of formula IIIa
- R4, R5 independently of each other aryl or hetaryl,
- m 0 or 1, where in the case of m equal 1 R2 is bound either to the 8 or 9 position of the perylene skeleton,
and the remaining variables R3, n and Y have the abovementioned meaning, and to compounds of general formula III per se;
to a process for the preparation of compounds of general formula IV - wherein the variables have the following meaning
- R13, R14 independently of each other aryl or hetaryl,
- Lg leaving group,
- m 0 or 1, where in the case of m equal 1 R14 is bound either to the 8 or 9
and the remaining variables R3, n and Y have the abovementioned meaning, and to compounds of general formula IV per se;
to the use of the compounds of general formulae II, III and IV each prepared according to the abovementioned processes and of compounds of general formulae II, III and IV per se for the preparation of dye-sensitized solar cells;
and to such dye-sensitized solar cells per se. - The direct conversion of solar energy to electrical energy in solar cells is based on the internal photoeffect of a semiconductor material, i.e. the generation of electron-hole pairs by absorption of photons and the separation of the negative and positive charge carriers at a p-n junction or a Schottky contact. The photovoltage thus generated can bring about a photocurrent in an external circuit, through which the solar cell delivers its power.
- Thin layers or films of metal oxides are known to constitute inexpensive solid semiconductor materials (n-semiconductors), but their absorption, owing to large band gaps, is typically not within the visible region of the electromagnetic spectrum. For use in solar cells, the metal oxides therefore have to be combined with a photosensitizer which absorbs in the wavelength range of sunlight, i.e. at from 300 to 2000 nm, 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 cell 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 zinc oxide, tin dioxide and especially titanium dioxide, which are used in the form of nanocrystalline 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 (DSCs) which are based on titanium dioxide as the semiconductor material are described, for example, in U.S. Pat. No. 4,927,721, Nature 353, p. 737-740 (1991) and U.S. Pat. No. 5,350,644, and also Nature 395, p. 583-585 (1998) and EP-A-1 176 646. These solar cells comprise monomolecular films of transition metal complexes, especially ruthenium complexes, which are bonded to the titanium dioxide layer via acid groups, as sensitizers and iodine/iodide redox systems present in dissolved form or amorphous organic p-conductors based on spirobifluorenes.
- Ruthenium complexes as molecular sensitizers have shown impressive solar-to-electric power conversion efficiencies (PCE) in liquid electrolyte based devices, with the PCE reaching over 11% under standard AM1.5G full sunlight as was shown by
- M. K. Nazeeruddin, F. De Angelis, S. Fantacci, A. Selloni, G. Viscardi, P. Liska, S. Ito, T. Bessho, M. G{umlaut over (r)}atzel, J. Am. Chem. Soc. 2005, 127, 16835;
- Y. Chiba, A. Islam, Y. Watanabe, R. Komiya, N. Koide, L. Y. Han, Jpn. J. Appl. Phys. 2006, 45, L638;
- F. Gao, Y. Wang, D. Shi, J. Zhang, M. K. Wang, X. Y. Jing, R. Humphry-Baker, P. Wang, S. M. Zakeeruddin, M. Grätzel, J. Am. Chem. Soc. 2008, 130, 10720;
- Y. M. Cao, Y. Bai, Q. J. Yu, Y. M. Cheng, S. Liu, D. Shi, F. Gao, P. Wang, J. Phys. Chem. C 2009, 113, 6290;
and - C.-Y. Chen, M. K. Wang, J.-Y. Li, N. Pootrakulchote, L. Alibabaei, C. H. Ngoc-le, J. D. Decoppet, J. H. Tsai, C. Gratzel, C. G. Wu, S. M. Zakeeruddin, M. G{umlaut over (r)}atzel, ACS Nano 2009, 3, 3103.
- In recent years, metal-free organic dyes have attracted increasing attention as they do not contain any toxic or costly metal and their properties are easily tuned by facile structural modification. In addition, they generally have much higher extinction coefficients when compared to Ru(II) polypyridyls, making them excellent for use in solid state DSCs in combination with hole transporting materials such as P3HT as shown, for example, by G. K. Mor, S. Kim, M. Paulose, O. K. Varghese, K. Shankar, J. Basham and C. A. Grimes, Nano Lett., 2009, 9, 4250, or spiro-MeOTAD as shown, for example, by H. J. Snaith, A. J. Moule, C. Klein, K. Meerholz, R. H. Friend, M. G{umlaut over (r)}atzel, Nano Lett., 2007, 7, 3372.
- Due to their high extinction coefficients and long-term stability against the action of oxygen and/or light rylene derivatives have attracted much attention as possible sensitizers for DSCs.
- Thus, perylene-3,4:9,10-tetracarboxylic acid derivatives as sensitizers are examined in Japanese documents JP-A-10-189065, 2000-243463, 2001-093589, 2000-100484 and 10-334954, and in New J. Chem. 26, p. 1155-1160 (2002).
- Further rylene derivatives useful as sensitizers in DSCs are prepared and evaluated in WO 2007/054470 A1.
- In order to facilitate tailor-made adjustments of the molecular properties of rylenes, versatile substitution patterns are desirable. To date most rylene derivatives exhibit substitution patterns on bay (1, 6, 7 and/or 12) and/or peri (3, 4, 9 and/or 10) positions as exemplified for the perylene skeleton:
- Examples of rylene compounds substituted on the edge (2, 5, 8 and/or 11) position are still scarce.
- Direct borylation of perylene in the 2,5,8,11-position is described by D. N. Coventry, A. S. Batsanov, A. E. Goeta, J. A. K. Howard, T. B. Marder and R. N. Perutz (Chem. Commun., 2005, 2172-2174).
- T. Teraoka, S. Hiroto and H. Shinokubo (Org. Lett. 2011, Vol. 13, No. 10, 2532-2535) and G. Battagliarin, C. Li, V. Enkelmann and K. Müllen (Org. Lett. 2011, Vol. 13, No. 12, 3012-3015) describe the preparation of the 2,5,8,11-tetraboronic ester perylenediimides
- by reacting an unsubstituted perylenediimide in the presence of an iridium or ruthenium catalyst, respectively, and bis(pinacolato)diboron, where Bpin/pinB stand for 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl substituents and R for hydrocarbon moieties.
- 2,5,8,11-tetrachloro, -tetrabromo and -tetracyano substituted perylenediimides and their preparation by reacting an unsubstituted perylenediimide with copper dichloride, copper dibromide and copper dicyanide, respectively, are disclosed by G. Battagliarin, Y. Zhao, C. Li and K. Müllen (Org. Lett. 2011, Vol. 13, No. 10, 3399-3401).
- Yet rylene 3,4-dicarboximide (perylene monoimide—PMI) derivatives which can be easily substituted on the edge (8 and/or 11) positions of the carbon skeleton are hitherto unknown.
- In view of the aforesaid it is the main object of the present invention to provide further convenient building blocks for the preparation of 8- and/or 11-substituted PMIs and 8- and/or 11-substituted PMIs per se for the application in DSCs which exhibit good to very good quantum efficiencies and very good medium to long term stabilities.
- Accordingly, compounds of general formula I
- have been synthesized,
wherein the variables have the following meaning - E1, E2 a moiety of formula Ia
- m 0 or 1, where in the case of m equal 1 E2 is bound either to the 8 or 9 position of the perylene skeleton and is identical to E1,
- W a bridging C2 or C3 moiety which may be substituted by one or more alkyl,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- and
- R12 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM, —SO3M or —PO3M,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different, and
- Z C1-C6-alkylene or 1,4-phenylene, where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
- Preferred compounds of general formula I are those wherein the variables have the following meaning
- E1, E2 a moiety selected from the group consisting of
- and the remaining variables m, R3, n and Y have the aforementioned meaning according to general formula I.
- Specifically preferred compounds are those wherein in general formula I the variables have the following meaning
- E1, E2 a moiety selected from the group consisting of
- m 0 or 1, where in the case of m equal 1 E2 is bound either to the 8 or 9 position of the perylene skeleton and is identical to E1,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- R12 alkyl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different and
- Z is C1-C6-alkylene or 1,4-phenylene.
- The aforementioned compounds of general formula I and their preferred embodiments are especially suited as building blocks for the preparation of 8,11- or 9,11-substituted perylene monoimides.
- A further objective of the instant invention is a process for the preparation of compounds of general formula I which comprises
- reacting a compound of general formula I*
- with a compound of general formula Ia*
- in the presence of bis(1,5-cyclooctadiene)dimethoxydiiridium ([Ir(OCH3)COD]2) and 4,4′-di-tert-butyl-2,2′-bipyridyl (dtbpy) in an inert solvent at ambient pressure and temperatures between 20° C. and the boiling point or the inert solvent at ambient pressure,
wherein the variables have the following meaning - W a bridging C2 or C3 moiety which may be substituted by one or more alkyl,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- and
- R12 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM, —SO3M or —PO3M,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different, and
- Z C1-C6-alkylene or 1,4-phenylene, where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
- A preferred process for the preparation of compounds of general formula I according to the instant invention comprises
- reacting a compound of general formula I*
- with a compound of general formula Ia* selected from the group consisting of
- in the presence of bis(1,5-cyclooctadiene)dimethoxydiiridium ([Ir(OCH3)COD]2) and 4,4′-di-tert-butyl-2,2′-bipyridyl (dtbpy) in an inert solvent at ambient pressure and temperatures between 20° C. and the boiling point or the inert solvent at ambient pressure,
wherein the variables have the following meaning - R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR2,
- and
- R12 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM, —SO3M or —PO3M,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different, and
- Z C1-C6-alkylene or 1,4-phenylene, where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
- A specifically preferred process for the preparation of compounds of general formula I according to the instant invention comprises
- reacting a compound of general formula I*
- with a compound of general formula Ia* selected from the group consisting of
- in the presence of bis(1,5-cyclooctadiene)dimethoxydiiridium ([Ir(OCH3)COD]2) and 4,4′-di-tert-butyl-2,2′-bipyridyl (dtbpy) in an inert solvent at ambient pressure and temperatures between 20° C. and the boiling point or the inert solvent at ambient pressure,
wherein the variables have the following meaning - m 0 or 1, where in the case of m equal 1 E2 is bound either to the 8 or 9 position of the perylene skeleton and is identical to E1,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- R12 alkyl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different and
- Z is C1-C6-alkylene or 1,4-phenylene.
- The term “ambient pressure” denotes basically unconfined reaction conditions, however, not excluding the application of protective gas atmosphere in order to avoid adverse effects by oxygen/air and/or moisture.
- “Inert solvent” means a solvent which does not contain moieties with either basic or acidic properties. Especially groups with acidic hydrogen atoms must not be present. In the case of a aromatic or heteroaromatic solvent this may only contain less than three neighboring hydrogen atoms directly bound to the carbon atoms or heteroatoms of the aromatic or heteroaromatic solvent skeleton in order to prevent the aromatic or heteroaromtic solvent from reacting with the boron containing educt. The term “inert solvent” is meant to embrace mixtures of inert solvents as well.
- Suitable inert solvents are e.g. dimethyl formamide (DMF), tetrahydofuran (THF), 1,4-dioxan, octane, hexane, pentane, mesitylene, pinacolone etc. and mixtures thereof.
- Further reaction conditions can easily be taken from D. N. Coventry, A. S. Batsanov, A. E. Goeta, J. A. K. Howard, T. B. Marder and R. N. Perutz, Chem. Commun., 2005, 2172-2174.
- A further objective of the instant invention is to provide a process for the preparation of compounds of general formula II
- wherein the variables have the following meaning
- Lg leaving group,
- m 0 or 1, where in the case of m equal 1 the one Lg is bound either to the 8 or 9 position of the perylene skeleton and is identical to the Lg bound to the 11 position,
and the remaining variables R3, n and Y have the meaning according to general formula I shown above and preferred embodiments thereof,
which comprises reacting a compound of general formula I or preferred embodiments thereof as described above or reacting a compound prepared according to the aforementioned process or preferred embodiments of said process with a compound Cu(Lg)2 in the presence of a polar solvent under confined conditions and temperatures between 20° C. and 140° C. - A preferred process according to the instant invention for the preparation of compounds of general formula II
- comprises reacting a compound of general formula I or preferred embodiments thereof as described above or reacting a compound prepared according to the aforementioned process or preferred embodiments of said process with a compound Cu(Lg)2 in the presence of a polar solvent under confined conditions and temperatures between 20° C. and 140° C.,
wherein the variables have the following meaning - Lg chlorine, bromine, iodine, brosylate, nosylate, tosylate, mesylate or triflate,
- m 0 or 1, where in the case of m equal 1 the one Lg is bound either to the 8 or 9 position of the perylene skeleton and is identical to the Lg bound to the 11 position,
and the remaining variables R3, n and Y have the meaning according to the compounds of general formula I described above and preferred embodiments thereof. - The term “confined conditions” refers to reaction conditions in which the reactants during the reaction are placed in a tightly sealed reaction vessel, ampoule or the like.
- “Polar solvent” typically refers to a solvent which is readily miscible with water. The term “polar solvent” is meant to embrace mixtures of polar solvents as well. Suitable polar solvents are e.g. water, dimethyl formamide (DMF), tetrahydofuran (THF), 1,4-dioxan, short carbon chain alcohols like e.g. butanol, i-butanol, tert.-butanol, propanol, i-propanol, ethanol or methanol and mixtures thereof.
- In general, the leaving group Lg can be any group known to a person skilled in the art as being prone to easily leave the molecule. Typically, Lg consists of or comprises strongly electron-withdrawing atoms or moieties and, thus, is normally split off as anionic species.
- Preferred groups Lg are chlorine, bromine, iodine, brosylate, nosylate, tosylate, mesylate and triflate which, in view of the aforesaid, leave the molecule as chloride, bromide, iodide, brosylate, nosylate, tosylate, mesylate (“mes”—H3C—SO3 −) or triflate (“tri”—F3C—SO3) anion.
- The structure of the brosylate (“bros”), nosylate (“nos”) and tosylate (“tos”) are, in respective order, as follows:
- Accordingly, preferred reagents Cu(Lg)2 are CuCl2, CuBr2, CuI2, Cu(bros)2, Cu(nos)2, Cu(tos)2, Cu(mes)2 and Cu(tri)2.
- Further reaction conditions can easily be taken from G. Battagliarin, Y. Zhao, C. Li and K. Müllen (Org. Lett. 2011, Vol. 13, No. 10, 3399-3401) and the respective references cited therein.
- A further objective of the instant invention are compounds of general formula II
- wherein the variables have the following meaning
- Lg leaving group,
- m 0 or 1, where in the case of m equal 1 the one Lg is bound either to the 8 or 9 position of the perylene skeleton and is identical to the Lg bound to the 11 position,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- and
- R12 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM, —SO3M or —PO3M,
- M hydrogen, alkali metal cation or [NR′]4*,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different, and
- Z C1-C6-alkylene or 1,4-phenylene, where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
- Preferred compounds according to the instant invention are of general formula II
- wherein the variables have the following meaning
- Lg chlorine, bromine, iodine, brosylate, nosylate, tosylate, mesylate or triflate,
- m 0 or 1, where in the case of m equal 1 the one Lg is bound either to the 8 or 9 position of the perylene skeleton and is identical to the Lg bound to the 11 position,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- R12 alkyl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different, and
- Z C1-C6-alkylene or 1,4-phenylene.
- A further objective of the instant invention is a process for the preparation of compounds of general formula III
- wherein the variables have the following meaning
- R1, R2 independently of each other a moiety of formula IIIa
- R4, R5 independently of each other aryl or hetaryl,
- m 0 or 1, where in the case of m equal 1 R2 is bound either to the 8 or 9 position of the perylene skeleton,
and the remaining variables R3, n and Y have the aforementioned meaning according to general formula II and its preferred embodiment
comprising
reacting a compound of general formula II or its preferred embodiment with a compound or a mixture of compounds of general formula IIIa* - in the presence of a palladium containing catalyst under the conditions of the Buchwald-Hartwig amination reaction.
- In a preferred process according to the instant invention for the preparation of compounds of general formula III the variables have the following meaning
- R1, R2 independently of each other halogen or a moiety of formula Ia
- m 0 or 1, where in the case of m equal 1 R2 is bound either to the 8 or 9 position of the perylene skeleton,
- R4, R5 independently of each other moieties of formulae Ib or Ic
- R6 hydrogen, alkyl, aryl, alkoxy, alkylthio or —NR7R8, where in case of two or more substituents (p equal or greater than 2) these may be identical or different,
- p 0, 1, 2, 3, 4 or 5,
- X C(R9R10)2, NR11, oxygen or sulfur,
- R7 to R11 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
and the remaining variables R3, n and Y have the aforementioned meaning according to general formula II and its preferred embodiment. - The Buchwald-Hartwig amination reaction is a well established synthetic route and the reaction conditions can easily be determined by a person skilled in the art. Conversion of aryl bromides to arylamines is specifically addressed in the publication by Guram, A. S.; Rennels, R. A.; Buchwald, S. L. (1995), “A Simple Catalytic Method for the Conversion of Aryl Bromides to Arylamines”, Angewandte Chemie International Edition 34 (12): 1348-1350.
- A further objective of the instant invention are compounds of general formula III
- wherein the variables have the following meaning
- R1, R2 independently of each other a moiety of formula IIIa
- R4, R5 independently of each other aryl or hetaryl,
- m 0 or 1, where in the case of m equal 1 the respective R2 is bound either to the 8 or 9 position of the perylene skeleton,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- and
- R12 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM, —SO3M or —PO3M,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different, and
- Z C1-C6-alkylene or 1,4-phenylene, where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
- Preferred compounds of general formula III
- are those in which the variables have the following meaning
- R1, R2 independently of each other a moiety of formula IIIa
- R4, R5 independently of each other aryl or hetaryl,
- m 0 or 1, where in the case of m equal 1 the respective R2 is bound either to the 8 or 9 position of the perylene skeleton,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- R12 alkyl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different, and
- Z C1-C6-alkylene or 1,4-phenylene.
- Further preferred compounds of general formula III
- are those in which the variables have the following meaning
- R1, R2 independently of each other halogen or a moiety of formula Ia
- m 0 or 1, where in the case of m equal 1 R2 is bound either to the 8 or 9 position of the perylene skeleton,
- R4, R5 independently of each other moieties of formulae Ib or Ic
- R6 hydrogen, alkyl, aryl, alkoxy, alkylthio or —NR7R8, where in case of two or more substituents (p equal or greater than 2) these may be identical or different,
- p 0, 1, 2, 3, 4 or 5,
- X C(R9R10)2, NR11, oxygen or sulfur,
- R7 to R11 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- and
- R12 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM, —SO3M or —PO3M,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different, and
- Z C1-C6-alkylene or 1,4-phenylene, where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
- Further preferred compounds of general formula III
- are those in which the variables have the following meaning
- R1, R2 independently of each other halogen or a moiety of formula Ia
- m 0 or 1, where in the case of m equal 1 R2 is bound either to the 8 or 9 position of the perylene skeleton,
- R4, R5 independently of each other moieties of formulae Ib or Ic
- R6 hydrogen, alkyl, aryl, alkoxy, alkylthio or —NR7R6, where in case of two or more substituents (p equal or greater than 2) these may be identical or different,
- p 0, 1, 2, 3, 4 or 5,
- X C(R9R10)2, NR11, oxygen or sulfur,
- R7 to R11 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- R12 alkyl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different, and
- Z C1-C6-alkylene or 1,4-phenylene.
- A further objective of the instant invention is a process for the preparation of compounds of general formula IV
- wherein the variables have the following meaning
- R13, R14 independently of each other aryl or hetaryl,
- Lg leaving group,
- m 0 or 1, where in the case of m equal 1 R14 is bound either to the 8 or 9 position of the perylene skeleton,
and the remaining variables R3, n and Y have the meaning according to general formula I and its preferred embodiments,
which comprises reacting a compound of general formula I or preferred embodiments of such compounds with compounds of general formula Lg-R13 and Lg-R14 in the presence of a palladium containing catalyst under the conditions of the Suzuki coupling reaction. - In a preferred embodiment of the aforementioned process the variables in general formula IV have the following meaning
- R13, R14 independently of each other moieties of formulae IVa or IVb
- R15 hydrogen, alkyl, aryl, alkoxy, alkylthio or —NR16R17, where in case of two or more substituents (q equal or greater than 2) these may be identical or different,
- q 0, 1, 2, 3, 4 or 5,
- X C(R18R19)2, NR20, oxygen or sulfur,
- R16 to R20 hydrogen, alkyl, aryl or hetaryl,
- m 0 or 1, where in the case of m equal 1 R14 is bound either to the 8 or 9 position of the perylene skeleton,
and the remaining variables R3, n and Y have the meaning according to general formula I and the preferred embodiments thereof. - In a specifically preferred process—also with reference to its aforementioned preferred embodiments—the variables Lg of Lg-R13 and Lg-R14 have the following meaning
- Lg chlorine, bromine, iodine, brosylate, nosylate, tosylate, mesylate or triflate,
- and the remaining variables have the aforementioned meaning with respect to the preferred embodiments.
- A further objective of the instant invention are compounds of general formula IV
- wherein the variables have the following meaning
- R13, R14 independently of each other aryl or hetaryl,
- m 0 or 1, where in the case of m equal 1 R14 is bound either to the 8 or 9 position of the perylene skeleton and is identical to R13,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- and
- R12 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM, —SO3M or —PO3M,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different, and
- Z C1-C6-alkylene or 1,4-phenylene, where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
- A further objective of the instant invention are compounds of general formula IV
- wherein the variables have the following meaning
- R13, R14 independently of each other aryl or hetaryl,
- m 0 or 1, where in the case of m equal 1 R14 is bound either to the 8 or 9 position of the perylene skeleton and is identical to R13,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- and
- R12 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM, —SO3M or —PO3M,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different, and
- Z C1-C6-alkylene or 1,4-phenylene, where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
- Preferred compounds of general formula IV
- are those in which the variables have the following meaning
- R13, R14 independently of each other aryl or hetaryl,
- m 0 or 1, where in the case of m equal 1 R14 is bound either to the 8 or 9 position of the perylene skeleton and is identical to R13,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- and
- R12 alkyl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different,
- Z C1-C6-alkylene or 1,4-phenylene.
- Further preferred compounds of general formula IV
- are those in which the variables have the following meaning
- R13, R14 independently of each other moieties of formulae IVa or IVb
- R15 hydrogen, alkyl, aryl, alkoxy, alkylthio or —NR16R17, where in case of two or more substituents (q equal or greater than 2) these may be identical or different,
- q 0, 1, 2, 3, 4 or 5,
- X C(R18R19)2, NR20, oxygen or sulfur,
- R16 to R20 hydrogen, alkyl, aryl or hetaryl,
- m 0 or 1, where in the case of m equal 1 R14 is bound either to the 8 or 9 position of the perylene skeleton and is identical to R13,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- and
- R12 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM, —SO3M or —PO3M,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different, and
- Z C1-C6-alkylene or 1,4-phenylene, where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen.
- Further preferred compounds of general formula IV
- are those in which the variables have the following meaning
- R13, R14 independently of each other moieties of formulae IVa or IVb
- R15 hydrogen, alkyl, aryl, alkoxy, alkylthio or —NR16R17, where in case of two or more substituents (q equal or greater than 2) these may be identical or different,
- q 0, 1, 2, 3, 4 or 5,
- X C(R18R19)2, NR20, oxygen or sulfur,
- R16 to R20 hydrogen, alkyl, aryl or hetaryl,
- m 0 or 1, where in the case of m equal 1 R14 is bound either to the 8 or 9 position of the perylene skeleton and is identical to R13,
- R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, diarylamino or dialkylamino,
- n 0, 1, 2, 3 or 4
- Y oxygen or NR12,
- and
- R12 alkyl,
- or
- a moiety of formula —Z-A, wherein
- A is —COOM,
- M hydrogen, alkali metal cation or [NR′]4+,
- R′ hydrogen or alkyl, where the radicals R′ may be identical or different,
- Z C1-C6-alkylene or 1,4-phenylene.
- A further objective or the instant invention is the use
- of compounds of general formula II prepared according to abovementioned process and its preferred embodiments,
of compounds of general formula III prepared according to the abovementioned process and its preferred embodiments,
of compounds of general formula IV prepared according to the abovementioned process and its preferred embodiments,
of compounds of general formula II and their preferred abovementioned embodiments,
of compounds of claim 12 and their preferred abovementioned embodiments and
of compounds of general formula IV and their preferred abovementioned embodiments for the preparation of dye-sensitized solar cells. - A further objective or the instant invention is a dye-sensitized solar cell comprising
- compounds of general formula III prepared according to the abovementioned process and its preferred embodiments,
compounds of general formula IV prepared according to the abovementioned process and its preferred embodiments,
compounds of general formula II and their preferred abovementioned embodiments, compounds of claim 12 and their preferred abovementioned embodiments or
compounds of general formula IV and their preferred abovementioned embodiments. - In the context of the present invention, alkyl, aryl or heteroaryl represents unsubstituted or substituted alkyl, unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl.
- Alkyl comprises straight-chain or branched alkyl. Alkyl is preferably C1-C30-alkyl, especially C1-C2-alkyl and most preferably C1-C12-alkyl. Examples of alkyl groups are especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.
- Further examples of branched alkyl groups can be represented by the following formula
- in which
- # denotes a bonding site, and
- Ra is selected from C1- to C28-alkyl, where the sum of the carbon atoms of the R9 radicals is an integer from 2 to 29.
- In the formula above, the Ra radicals are preferably selected from C1- to C12-alkyl, especially C1- to C8-alkyl.
- Preferred branched alkyl radicals of the above formula are, for example:
- 1-ethylpropyl, 1-methylpropyl, 1-propylbutyl, 1-ethylbutyl, 1-methylbutyl, 1-butylpentyl, 1-propylpentyl, 1-ethylpentyl, 1-methylpentyl, 1-pentylhexyl, 1-butylhexyl, 1-propylhexyl, 1-ethylhexyl, 1-methylhexyl, 1-hexylheptyl, 1-pentylheptyl, 1-butylheptyl, 1-propylheptyl, 1-ethylheptyl, 1-methylheptyl, 1-heptyloctyl, 1-hexyloctyl, 1-pentyloctyl, 1-butyloctyl, 1-propyloctyl, 1-ethyloctyl, 1-methyloctyl, 1-octylnonyl, 1-heptylnonyl, 1-hexylnonyl, 1-pentylnonyl, 1-butylnonyl, 1-propylnonyl, 1-ethylnonyl, 1-methylnonyl, 1-nonyldecyl, 1-octyldecyl, 1-heptyldecyl, 1-hexyldecyl, 1-pentyldecyl, 1-butyldecyl, 1-propyldecyl, 1-ethyldecyl, 1-methyldecyl, 1-decylundecyl, 1-nonylundecyl, 1-octylundecyl, 1-heptylundecyl, 1-hexylundecyl, 1-pentylundecyl, 1-butylundecyl, 1-propylundecyl, 1-ethylundecyl, 1-methylundecyl, 1-undecyldodecyl, 1-decyldodecyl, 1-nonyldodecyl, 1-octyldodecyl, 1-heptyldodecyl, 1-hexyldodecyl, 1-pentyldodecyl, 1-butyldodecyl, 1-propyldodecyl, 1-ethyldodecyl, 1-methyldodecyl, 1-dodecyltridecyl, 1-undecyltridecyl, 1-decyltridecyl, 1-nonyltridecyl, 1-octyltridecyl, 1-heptyltridecyl, 1-hexyltridecyl, 1-pentyltridecyl, 1-butyltridecyl, 1-propyltridecyl, 1-ethyltridecyl, 1-methyltridecyl, 1-tridecyltetradecyl, 1-undecyltetradecyl, 1-decyltetradecyl, 1-nonyltetradecyl, 1-octyltetradecyl, 1-heptyltetradecyl, 1-hexyltetradecyl, 1-pentyltetradecyl, 1-butyltetradecyl, 1-propyltetradecyl, 1-ethyltetradecyl, 1-methyltetradecyl, 1-pentadecylhexadecyl, 1-tetradecylhexadecyl, 1-tridecylhexadecyl, 1-dodecylhexadecyl, 1-undecylhexadecyl, 1-decylhexadecyl, 1-nonylhexadecyl, 1-octylhexadecyl, 1-heptylhexadecyl, 1-hexylhexadecyl, 1-pentylhexadecyl, 1-butylhexadecyl, 1-propylhexadecyl, 1-ethylhexadecyl, 1-methylhexadecyl, 1-hexadecyloctadecyl, 1-pentadecyloctadecyl, 1-tetradecyloctadecyl, 1-tridecyloctadecyl, 1-dodecyloctadecyl, 1-undecyloctadecyl, 1-decyloctadecyl, 1-nonyloctadecyl, 1-octyloctadecyl, 1-heptyloctadecyl, 1-hexyloctadecyl, 1-pentyloctadecyl, 1-butyloctadecyl, 1-propyloctadecyl, 1-ethyloctadecyl, 1-methyloctadecyl, 1-nonadecyleicosanyl, 1-octadecyleicosanyl, 1-heptadecyleicosanyl, 1-hexadecyleicosanyl, 1-pentadecyleicosanyl, 1-tetradecyleicosanyl, 1-tridecyleicosanyl, 1-dodecyleicosanyl, 1-undecyleicosanyl, 1-decyleicosanyl, 1-nonyleicosanyl, 1-octyleicosanyl, 1-heptyleicosanyl, 1-hexyleicosanyl, 1-pentyleicosanyl, 1-butyleicosanyl, 1-propyleicosanyl, 1-ethyleicosanyl, 1-methyleicosanyl, 1-eicosanyldocosanyl, 1-nonadecyldocosanyl, 1-octadecyldocosanyl, 1-heptadecyldocosanyl, 1-hexadecyldocosanyl, 1-pentadecyldocosanyl, 1-tetradecyldocosanyl, 1-tridecyldocosanyl, 1-undecyldocosanyl, 1-decyldocosanyl, 1-nonyldocosanyl, 1-octyldocosanyl, 1-heptyldocosanyl, 1-hexyldocosanyl, 1-pentyldocosanyl, 1-butyldocosanyl, 1-propyldocosanyl, 1-ethyldocosanyl, 1-methyldocosanyl, 1-tricosanyltetracosanyl, 1-docosanyltetracosanyl, 1-nonadecyltetracosanyl, 1-octadecyltetracosanyl, 1-heptadecyltetracosanyl, 1-hexadecyltetracosanyl, 1-pentadecyltetracosanyl, 1-pentadecyltetracosanyl, 1-tetradecyltetracosanyl, 1-tridecyltetracosanyl, 1-dodecyltetracosanyl, 1-undecyltetracosanyl, 1-decyltetracosanyl, 1-nonyltetracosanyl, 1-octyltetracosanyl, 1-heptyltetracosanyl, 1-hexyltetracosanyl, 1-pentyltetracosanyl, 1-butyltetracosanyl, 1-propyltetracosanyl, 1-ethyltetracosanyl, 1-methyltetracosanyl, 1-heptacosanyloctacosanyl, 1-hexacosanyloctacosanyl, 1-pentacosanyloctacosanyl, 1-tetracosanyloctacosanyl, 1-tricosanyloctacosanyl, 1-docosanyloctacosanyl, 1-nonadecyloctacosanyl, 1-octadecyloctacosanyl, 1-heptadecyloctacosanyl, 1-hexadecyloctacosanyl, 1-hexadecyloctacosanyl, 1-pentadecyloctacosanyl, 1-tetradecyloctacosanyl, 1-tridecyloctacosanyl, 1-dodecyloctacosanyl, 1-undecyloctacosanyl, 1-decyloctacosanyl, 1-nonyloctacosanyl, 1-octyloctacosanyl, 1-heptyloctacosanyl, 1-hexyloctacosanyl, 1-pentyloctacosanyl, 1-butyloctacosanyl, 1-propyloctacosanyl, 1-ethyloctacosanyl, 1-methyloctacosanyl.
- Alkyl also comprises alkyl radicals whose carbon chains may be interrupted by one or more nonadjacent groups selected from oxygen, sulfur, —CO—, —NRb—, —SO— and/or —SO2— where Rb is preferably hydrogen, unsubstituted straight-chain or branched alkyl as described before or unsubstituted aryl as described below.
- Substituted alkyl groups may, depending on the length of the alkyl chain, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro.
- Aryl-substituted alkyl radicals (aralkyl) have at least one unsubstituted or substituted aryl group, as defined below. The alkyl group of the aralkyl radical may bear at least one further substituent and/or be interrupted by one or more nonadjacent groups selected from oxygen, sulfur, —CO—, —NRb-, —SO— and/or —SO2— where Rb is preferably hydrogen, unsubstituted straight-chain or branched alkyl as described before or unsubstituted aryl as described below. Arylalkyl is preferably phenyl-C1-C10-alkyl, more preferably phenyl-C1-C4-alkyl, for example benzyl, 1-phenethyl, 2-phenethyl, 1-phenprop-1-yl, 2-phenprop-1-yl, 3-phenprop-1-yl, 1-phenbut-1-yl, 2-phenbut-1-yl, 3-phenbut-1-yl, 4-phenbut-1-yl, 1-phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl, 4-phenbut-2-yl, 1-(phenmeth)eth-1-yl, 1-(phenmethyl)-1-(methyl)eth-1-yl or -(phenmethyl)-1-(methyl)prop-1-yl; preferably benzyl and 2-phenethyl.
- Halogen-substituted alkyl groups (haloalkyl) comprise a straight-chain or branched alkyl group in which at least one hydrogen atom or all hydrogen atoms are replaced by halogen. The halogen atoms are preferably selected from fluorine, chlorine and bromine, especially fluorine and chlorine. Examples of haloalkyl groups are especially chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, —CH2—C2F5, —CF2—C2F5, —CF(CF3)2, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, nonafluorobutyl, 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl, 5,5,5-trichloro-1-pentyl, undecafluoropentyl, 6-fluoro-1-hexyl, 6-chloro-1-hexyl, 6-bromo-1-hexyl, 6-iodo-1-hexyl, 6,6,6-trichloro-1-hexyl or dodecafluorohexyl.
- The above remarks regarding unsubstituted or substituted alkyl also apply to unsubstituted or substituted alkoxy and unsubstituted or substituted dialkylamino.
- Specific examples of unsubstituted and substituted alkyl radicals which may be interrupted by one or more nonadjacent groups selected from oxygen, sulfur, —NRb—, —CO—, —SO— and/or —SO2— are:
- methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-propoxypropyl, 3-butoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 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-butylthioethyl, 3-methylthiopropyl, 3-ethylthiopropyl, 3-propylthiopropyl, 3-butylthiopropyl, 4-methylthiobutyl, 4-ethylthiobutyl, 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-trithiaundecyl, 3,6,9-trithiadodecyl, 3,6,9,12-tetrathiatridecyl and 3,6,9,12-tetrathiatetradecyl;
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-diazaoctyl, 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;
(1-ethylethylidene)aminoethylene, (1-ethylethylidene)aminopropylene, (1-ethylethylidene)aminobutylene, (1-ethylethylidene)aminodecylene and (1-ethylethylidene)aminododecylene;
propan-2-on-1-yl, butan-3-on-1-yl, butan-3-on-2-yl and 2-ethylpentan-3-on-1-yl;
2-methylsulfinylethyl, 2-ethylsulfinylethyl, 2-propylsulfinylethyl, 2-isopropylsulfinylethyl, 2-butylsulfinylethyl, 2- and 3-methylsulfinylpropyl, 2- and 3-ethylsulfinylpropyl, 2- and 3-propylsulfinylpropyl, 2- and 3-butylsulfinylpropyl, 2- and 4-methylsulfinylbutyl, 2- and 4-ethylsulfinylbutyl, 2- and 4-propylsulfinylbutyl and 4-butylsulfinylbutyl;
2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl, 2-isopropylsulfonylethyl, 2-butylsulfonylethyl, 2- and 3-methylsulfonylpropyl, 2- and 3-ethylsulfonylpropyl, 2- and 3-propylsulfonylpropyl, 2- and 3-butylsulfonylpropyl, 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-carboxyoctyl, 10-carboxydecyl, 12-carboxydodecyl and 14-carboxyltetradecyl;
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, 3- and 4-hydroxybutyl and 8-hydroxyl-4-oxaoctyl;
2-cyanoethyl, 3-cyanopropyl, 3- and 4-cyanobutyl;
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, butoxy, pentoxy and hexoxy;
methylthio, ethylthio, propylthio, butylthio, pentylthio and hexylthio;
methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, dicyclopentylamino, dicyclohexylamino, dicycloheptylamino, diphenylamino and dibenzylamino;
formylamino, acetylamino, propionylamino and benzoylamino;
carbamoyl, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl, heptylaminocarbonyl, octylaminocarbonyl, nonylaminocarbonyl, decylaminocarbonyl and phenylamino-carbonyl;
aminosulfonyl, n-dodecylaminosulfonyl, N,N-diphenylaminosulfonyl, and N,N-bis(4-chlorophenyl)aminosulfonyl;
methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl hexoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenoxycarbonyl, (4-tert-butylphenoxy)carbonyl and (4-chlorophenoxy)carbonyl;
methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, butoxysulfonyl, hexoxysulfonyl, dodecyloxysulfonyl and octadecyloxysulfonyl. - In the context of the invention, cycloalkyl denotes a cycloaliphatic radical having preferably 3 to 10, more preferably 5 to 8, carbon atoms. Examples of cycloalkyl groups are especially cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
- Substituted cycloalkyl groups may, depending on the ring size, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro. In the case of substitution, the cycloalkyl groups preferably bear one or more, for example one, two, three, four or five, C1-C6-alkyl groups. Examples of substituted cycloalkyl groups are especially 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 2-, 3- and 4-propylcyclohexyl, 2-, 3- and 4-isopropylcyclohexyl, 2-, 3- and 4-butylcyclohexyl, 2-, 3- and 4-sec.-butylcyclohexyl, 2-, 3- and 4-tert-butylcyclohexyl, 2-, 3- and 4-methylcycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 2-, 3- and 4-propylcycloheptyl, 2-, 3- and 4-isopropylcycloheptyl, 2-, 3- and 4-butylcycloheptyl, 2-, 3- and 4-sec-butylcycloheptyl, 2-, 3- and 4-tert-butylcycloheptyl, 2-, 3-, 4- and 5-methylcyclooctyl, 2-, 3-, 4- and 5-ethylcyclooctyl, 2-, 3-, 4- and 5-propylcyclooctyl.
- Specific examples of substituted and unsubstituted cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclo-pentyl, 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-methyl-cycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 3- and 4-propylcycloheptyl, 3- and 4-iso-propylcycloheptyl, 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;
- In the context of the present invention, aryl comprises mono- or polycyclic aromatic hydrocarbon radicals and monocyclic aromatic hydrocarbon radicals which may be fused to one or more unfused or fused saturated or unsaturated carbocyclic or heterocyclic five or six membered rings. Aryl has preferably 6 to 14, more preferably 6 to 10, carbon atoms. Examples of aryl are especially phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl and pyrenyl, especially phenyl, naphthyl and fluorenyl.
- Substituted aryls may, depending on the number and size of their ring systems, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro. The alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl and hetaryl substituents on the aryl may in turn be unsubstituted or substituted. Reference is made to the substituents mentioned above for these groups. The substituents on the aryl are preferably selected from alkyl, alkoxy, haloalkyl, haloalkoxy, aryl, fluorine, chlorine, bromine, cyano and nitro. Substituted aryl is more preferably substituted phenyl which generally bears 1, 2, 3, 4 or 5, preferably 1, 2 or 3, substituents.
- Substituted aryl is preferably aryl substituted by at least one alkyl group (“alkaryl”). Alkaryl groups may, depending on the size of the aromatic ring system, have one or more (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more than 9) alkyl substituents. The alkyl substituents may be unsubstituted or substituted. In this regard, reference is made to the above statements regarding unsubstituted and substituted alkyl. In a preferred embodiment, the alkaryl groups have exclusively unsubstituted alkyl substituents. Alkaryl is preferably phenyl which bears 1, 2, 3, 4 or 5, preferably 1, 2 or 3, more preferably 1 or 2, alkyl substituents.
- Aryl which bears one or more radicals is, for example, 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3- and 4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-sec-butylphenyl, 2,4,6-tri-sec-butylphenyl, 2-, 3- and 4-tert-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-tert-butylphenyl and 2,4,6-tri-tert-butylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and 4-isopropoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropoxyphenyl and 2-, 3- and 4-butoxyphenyl; 2-, 3- and 4-cyanophenyl.
- The above remarks regarding unsubstituted or substituted aryl also apply to unsubstituted or substituted aryloxy and unsubstituted or substituted arylthio. Examples of aryloxy are phenoxy and naphthyloxy.
- In the context of the present invention, hetaryl comprises heteroaromatic, mono- or polycyclic groups and monocyclic groups which may be fused to one or more unfused or fused saturated or unsaturated carbocyclic or heterocyclic five or six membered rings. In addition to the ring carbon atoms, these have 1, 2, 3, 4 or more than 4 of the ring heteroatoms. The heteroatoms are preferably selected from oxygen, nitrogen, selenium and sulfur. The hetaryl groups have preferably 5 to 18, e.g. 5, 6, 8, 9, 10, 11, 12, 13 or 14, ring atoms.
- Monocyclic hetaryl groups are preferably 5- or 6-membered hetaryl groups, such as 2-furyl (furan-2-yl), 3-furyl (furan-3-yl), 2-thienyl (thiophen-2-yl), 3-thienyl (thiophen-3-yl), selenophen-2-yl, selenophen-3-yl, 1H-pyrrol-2-yl, 1H-pyrrol-3-yl, pyrrol-1-yl, imidazol-2-yl, imidazol-1-yl, imidazol-4-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 4H-[1,2,4]-triazol-3-yl, 1,3,4-triazol-2-yl, 1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl.
- Polycyclic hetaryl has 2, 3, 4 or more than 4 fused rings. The fused-on rings may be aromatic, saturated or partly unsaturated. Examples of polycyclic hetaryl groups are quinolinyl, isoquinolinyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, benzoxazolyl, benzisoxazolyl, benzthiazolyl, benzoxadiazolyl; benzothiadiazolyl, benzoxazinyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, benzotriazinyl, benzoselenophenyl, thienothiophenyl, thienopyrimidyl, thiazolothiazolyl, dibenzopyrrolyl (carbazolyl), dibenzofuranyl, dibenzothiophenyl, naphtho[2,3-b]thiophenyl, naphtha[2,3-b]furyl, dihydroindolyl, dihydroindolizinyl, dihydroisoindolyl, dihydroquinolinyl, dihydroisoquinolinyl.
- Substituted heteroaryls may, depending on the number and size of their ring systems, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro. Halogen substituents are preferably fluorine, chlorine or bromine. The substituents are preferably selected from C1-C6-alkyl, C1-C6-alkoxy, hydroxyl, carboxyl, halogen and cyano.
- The above remarks regarding unsubstituted or substituted heteroaryl also apply to unsubstituted or substituted heteroaryloxy and unsubstituted or substituted heteroarylthio.
- Halogen represents fluorine, chlorine, bromine or iodine, preferably chlorine and bromine.
- Alkali cation represents sodium, potassium, rubidium and cesium, preferably sodium and potassium.
- R′ in the tetraalkyl ammonium cation [NR′]4+ typically refers to methyl or tert.-butyl.
- Further details on the preparation of the compounds according to the instant invention can be taken from the experimental section.
- DSCs generally comprise the following elements: an electrically conductive layer (being part of or forming the working electrode or anode), a photosensitive layer generally comprising a semiconductive metal oxide and a photosensitive dye, a charge transfer layer and another electrically conductive layer (being part of or forming the counter electrode or cathode).
- Regarding further details of the construction of DSCs particular reference is made to WO 2012/001628 A1, which is hereby fully incorporated by reference.
- A1) Preparation of compounds or general formula I according to the invention
-
- N-(1-ethylpropyl)-2,5-bis[3,3-dimethylbutyl]perylene-3,4-dicarboxylic acid monoimide (0.100 g, 0.179 mmol), bis(pinacolato)diboron (0.100 g, 0.393 mmol), [Ir(OMe)cod]2 (bis(1,5-cyclooctadiene)dimethoxydiiridium; 5.9 mg, 8.9 μmol) and dtbpy (4,4′-di-tert-butyl-2,2′-bipyridyl; 4.8 mg, 17.9 μmol) were mixed in an oven dried flask under argon atmosphere. Anhydrous cyclohexane (3 ml) was added and the reaction heated for 1 hour at 80° C. in a microwave oven. After cooling down to room temperature, the solvent was evaporated and the solid purified by column chromatography (silica gel, first CH2Cl2/AcOEt 50/1 and afterwards CH2Cl2/acetone/MeOH 30/5/1). The desired compound C1 was obtained as an orange solid in 74% yield (0.107 g, 0.132 mmol).
- 1H NMR (250 MHz, CD2Cl2) δ [ppm]: 8.78 (s, 2H), 8.40 (s, 2H), 8.26 (s, 2H), 5.19-4.99 (m, 1H), 3.47 (dt, J=24.7, 10.7 Hz, 4H), 2.44-2.16 (m, 2H), 2.00-1.77 (m, 2H), 1.65-1.52 (m, 4H), 1.44 (s, 24H), 1.09 (s, 18H), 0.92 (t, J=7.4 Hz, 6H).
- 13C NMR (63 MHz, CD2Cl2) δ [ppm]: 165.41, 152.04, 139.48, 135.78, 133.66, 133.27, 131.54, 129.38, 129.15, 128.33, 125.38, 125.36, 119.57, 85.18, 57.55, 46.55, 33.15, 31.59, 30.00, 25.91, 25.56, 11.99.
- FD Mass Spectrum (8 kV): m/z=815.0 (100%) [M+]
-
- N-(1-ethylpropyl) perylene-3,4-dicarboxylic acid monoimide (2.00 g, 5.11 mmol), bispinacolondiboronate (3.11 g, 12.26 mmol), [Ir(OMe)cod]2 (0.169 g, 0.255 mmol) and dtbpy (0.137 g, 0.511 mmol) were mixed in an oven dried flask under argon atmosphere. Anhydrous tetrahydrofuran (THF; 80 ml) was added and the reaction heated for 18 hours at 60° C. The solvent was evaporated and the reaction mixture dissolved in dichloromethane, precipitated in methanol and filtered. The process was repeated three times and the solid so obtained afterwards purified by GPC column (dichlormethane, Bio-Beads S-X1 Beads 200-400 mesh). The desired product C2 was obtained as a red solid (68% yield, 2.24 g, 3.47 mmol).
- 1H NMR (250 MHz, CD2Cl2) δ [ppm]: 8.78 (s, 2H), 8.57-8.44 (m, 4H), 8.35 (s, 2H), 5.15-4.94 (m, 1H), 2.40-2.15 (m, 2H), 2.02-1.78 (m, 2H), 1.44 (s, 24H), 0.91 (t, J=7.5 Hz, 6H).
- 13C NMR (63 MHz, CD2Cl2) δ [ppm]: 164.87, 139.54, 137.40, 133.52, 132.75, 131.16, 130.58, 129.90, 128.82, 128.24, 127.32, 121.72, 120.86, 84.97, 57.64, 25.56, 25.33, 11.71.
- FD Mass Spectrum (8 kV): m/z=642.6 (100%) [M+]
- UV-vis (in toluene): λmax (ε[M−1 cm−1]): 481 nm (2.98×104 M−1 cm−1), 509 nm (2.83×104 M−1 cm−1). The monoborylated compound (also according to general formula I of the present invention)
- was obtained as by-product but not characterized further.
-
- N-(1-heptyloctyl)-perylene-3,4-dicarboxylic acid monoimide (0.76 g, 1.42 mmol), bispinacolondiboronate (0.87 g, 3.43 mmol), [Ir(OMe)cod]2 (0.047 g, 0.255 mol) and dtbpy (0.137 g, 0.511 mmol) were mixed in an oven dried flask under argon atmosphere. Anhydrous THF (80 ml) was added and the reaction heated for 18 hours at 60° C. the solvent was evaporated and the reaction mixture dissolved in dichloromethane, precipitated in methanol and filtered. The process was repeated three times and the solid so obtained afterwards purified by GPC column (dichlormethane, Bio-Beads S-X1 Beads 200-400 mesh). The desired product C3 was obtained as a red solid (71% yield, 2.24 g, 3.47 mmol).
- 1H NMR (250 MHz, CD2Cl2) δ [ppm]: 8.51 (s, 2H), 8.34 (d, J=5.5 Hz, 2H), 8.23 (d, J=8.2 Hz, 2H), 8.16 (s, 2H), 5.20 (tt, J=9.2, 5.9 Hz, 1H), 2.41-2.17 (m, 4H), 1.98-1.81 (m, 2H), 1.48 (s, 24H), 1.41-1.12 (m, 20H), 0.84 (t, J=6.6 Hz, 6H).
- 13C NMR (63 MHz, CD2Cl2) δ [ppm]: 165.29, 164.35, 139.36, 137.04, 133.18, 131.87, 131.15, 130.75, 130.27, 129.55, 128.45, 128.12 126.97, 122.01, 121.21, 120.61, 84.93, 54.61, 32.98, 32.47, 30.24, 29.91, 27.67, 25.44, 23.24, 14.46.
- A2) Preparation of compounds or general formula II according to the invention:
-
- N-(1-ethylpropyl)-8, 11-bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-y]-perylene-3,4-dicarboxylic acid monoimide (0.600 g, 0.933 mmol) was suspended in a mixture of dioxane (100 ml), methanol (10 ml) and water (10 ml) in a 210 mL pressure vial. Copper(II) bromide (2.08 g, 9.33 mmol) was added, the vessel sealed and heated up to 120° C. for 12 hours. The reaction mixture was poured into 200 mL of 1.0 M hydrochloric acid and filtered to obtain a red solid. The desired compound C4 was obtained after column chromatography (silica, toluene) and crystallization from toluene as an orange solid (yield 48%, 0.25 g, 0.48 mmol).
- 1H NMR (500 MHz, 373 K, C2Cl4D2) δ [ppm]: 8.64 (d, J=5.2 Hz, 2H), 8.50 (s, 2H), 8.43 (d, J=6.0 Hz, 2H), 7.98 (s, 2H), 5.20-4.94 (m, 1H), 2.35-2.21 (m, 2H), 2.08-1.95 (m, 2H), 1.03-0.96 (m, 6H).
- 13C NMR (126 MHz, D2SO4) δ [ppm]: 164.68, 164.42, 148.77, 148.62, 145.82, 143.72, 143.53, 139.88, 138.98, 138.17, 135.49, 131.55, 128.93, 126.02, 125.57, 125.46, 125.39, 122.74, 112.08, 111.88, 71.63, 25.65, 11.14 (Signal at 11.14 set as reference using the chemical shift of the same carbon obtained from a 13C NMR in tetrachloroethane).
- FD Mass Spectrum (8 kV): m/z=549.6 (100%) [M+]
- UV-vis (in toluene): λmax (ε[M−1 cm−1]): 495 nm (3.21×104 M−1 cm−1), 466 nm (2.45×104 M−1 cm−1).
- The monobrominated compound (also according to general formula II of the present invention)
- was obtained as by-product but not characterized further.
-
- N-(1-heptyloctyl)-8,11-bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-y]-perylene-3,4-dicarboxylic acid monoimide (1.00 g, 1.28 mmol) was suspended in a mixture of THF (90 ml), methanol (10 ml) and water (10 ml) in a 210 mL pressure vial. Copper(II) bromide (2.85 g, 12.8 mmol) was added, the vessel sealed and heated up to 120° C. for 12 hours. The reaction mixture was poured into 200 mL of 1.0 M hydrochloric acid and filtered to obtain a red solid. The desired compound C5 was obtained after column chromatography (silica, toluene) and obtained as a bright orange solid (yield 38%, 0.34 g, 0.49 mmol).
- 1H NMR (500 MHz, CD2Cl2) δ [ppm]: 8.32 (s, br, 2H), 7.80 (d, J=8.0 Hz, 2H), 7.73 (s, 2H), 7.35 (s, 2H), 5.21-5.06 (m, 1H), 2.31-2.17 (m, 2H), 1.94-1.77 (m, 2H), 1.42-1.20 (m, 20H), 0.86 (t, J=6.6 Hz, 6H)
- 13C NMR (126 MHz, CD2Cl2) δ [ppm]: 164.97, 136.25, 134.15, 131.68, 131.11, 130.83, 129.68, 126.16, 126.11, 124.73, 123.44, 122.45, 121.23, 54.94, 32.94, 32.45, 30.16, 29.89, 27.73, 23.23, 14.45.
- FD Mass Spectrum (8 kV): m/z=549.6 (100%) [M+]
- UV-vis (in toluene): λmax (ε[M−1 cm−1]): 496 nm (3.68×104 M−1 cm−1), 467 nm (2.84×104 M−1 cm−1).
-
- N-(1-ethylpropyl)-8,11-bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-y]-perylene-3,4-dicarboxylic acid monoimide (0.600 g, 0.933 mmol) was suspended in a mixture of dioxane (100 ml), methanol (10 ml) and water (10 ml) in a 210 mL pressure vial. Copper(II) chloride (1.254 g, 9.33 mmol) was added, the vessel sealed and heated up to 120° C. for 12 hours. The reaction mixture was poured into 200 mL of 1.0 M hydrochloric acid and filtered to obtain a red solid. The desired compound C6 was obtained after column chromatography (silica, toluene) and crystallization from toluene as a dark orange solid (yield 54%, 0.23 g, 0.50 mmol).
- 1H NMR (250 MHz, C2D2Cl4) δ [ppm]: 8.51 (d, J=8.0 Hz, 2H), 8.26 (d, J=8.2 Hz, 2H), 8.13 (d, J=1.7 Hz, 2H), 7.62 (d, J=1.5 Hz, 2H), 4.98 (d, J=6.0 Hz, 1H), 2.31-2.08 (m, 2H), 2.02-1.81 (m, 2H), 0.89 (t, J=7.4 Hz, 6H).
- 13C NMR (126 MHz, D2SO4) δ [ppm]: 164.71, 164.44, 149.05, 148.92, 140.44, 138.95, 138.38, 138.12, 137.19, 135.23, 131.65, 128.97, 126.12, 125.49, 122.43, 112.07, 111.77, 71.79, 25.68, 11.15 (signal at 11.15 set as reference using the chemical shift of the same carbon obtained from a 13C NMR in tetrachloroethane).
- FD Mass Spectrum (8 kV): m/z=460.6 (100%) [M+]
- UV-vis (in toluene): λmax (ε[M−1 cm1]): 494 nm (2.61×104 M−1 cm−1), 465 nm (2.00×104 M−1 cm−1).
- The monochlorinated compound (also according to general formula II of the present invention)
- was obtained as by-product but not characterized further.
A3) Preparation of compounds or general formula III according to the invention: -
- 1.4 g of 9-(bis(4-(2,4,4-trimethylpentane-2-yl)phenyl)amino-perylene-3,4-dicarboxy anhydride (synthesis according to the procedure presented in Li, C. “Novel Functional Rylene Dyes for Dye-Sensitized Solar Cells”, Ph.D. thesis, Johannes-Gutenberg-Universität Mainz, 2008), 684 mg of pentan-3-amine (7.86 mol) and 20 g of imidazole (0.29 mol) were mixed in a Schlenk tube and stirred under argon at 140° C. overnight. After cooling down dilute hydrochloric acid was added. The blue precipitate was filtered and washed with water. The crude product C7 was purified by column chromatography on silica gel with dichloromethane and petrol ether (3:2).
- Yield: 1.4 g blue solid (91%)
- 1H NMR (300 MHz, THF, 298 K) δ [ppm]: 8.51-8.36 (m, 6H), 7.88 (d, J=8.4, 1H), 7.38-7.12 (m, 6H), 6.87 (d, J=8.6, 4H), 5.05-4.88 (m, 1H), 2.29-2.07 (m, 2H), 1.88-1.69 (m, 2H), 1.33-1.16 (m, 12H), 0.78 (t, J=7.4, 6H), 0.66 (s, 18H).
- 13C NMR (75 MHz, THF, 298 K) δ [ppm]: 147.30, 146.07, 144.01, 136.81, 136.72, 131.00, 129.97, 129.86, 129.82, 127.51, 127.01, 126.49, 126.38, 126.30, 126.20, 124.65, 123.94, 122.31, 120.13, 119.77, 56.85, 56.64, 37.88, 32.07, 31.21, 30.97, 10.66.
- IR spectrum (ATR) λmax [cm−1]=3034, 2953, 2874, 2691, 1652, 1593, 1566, 1500, 1457, 1349, 1268, 1246, 1197, 1085, 808, 751.
- UV-Vis spectrum (CH2Cl2): λmax [nm] (ε[M−1 cm−1])=578 (30,907).
- High Resolution Mass (ESI): [M]+: calculated: 782.481. found: 782.4789, discrepancy: −2.8 ppm. The triphenylamine moiety is losing an electron to form [M]+ as well as [M+H]+.
- Elemental analysis (C55H62N2O2): calculated: 84.36%; C, 7.98%; H, 3.58%; N, % S. found: 84.25%; C, 7.62%; H, 3.75%; N, % S.
-
- 1 g of N-(1′-ethylpropyl)-9-(bis(4-(2,4,4-trimethylpentane-2-yl)phenylamino-perylene-3,4-dicarboximide (2.28 mmol) and 360 mg of 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (1.40 mmol), 42 mg of bis(1,5-cyclooctadiene)dimethoxydiiridium (0.065 mmol), and 34 mg of 4,4′-di-tert-butyl-2,2′-bipyridyl (0.119 mmol) were dissolved in 70 mL of dry THF under argon and stirred overnight at 60° C., however not leading to full conversion of the starting material. Both starting material and product show similar intensities on a silica thin layer chromatography plate in dichloromethane.
- The solvent was removed under reduced pressure, the reaction mixture solved in dichloromethane, washed with water and dried over magnesium sulfate. It was then used without further purification for the next step.
- 900 mg of the mixture of N-(1′-ethylpropyl)-8-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-10-(bis(4-(2,4,4-trimethylpentane-2-yl)phenyl)amino-perylene-3,4-dicarboximide and N-(1′-ethylpropyl)-9-(bis(4-(2,4,4-trimethylpentane-2-yl)phenyl)amino-perylene-3,4-dicarboximide were dissolved in 16 mL of 1,4-dioxane, 2 mL of methanol and 2 mL of water in a pressure vial. 1.1 g of copper(II)bromide (4.95 mmol) were added and the mixture was stirred over night at 120° C. After cooling down, the reaction mixture was roughly purified via column chromatographyon silica gel with dichloromethane giving a mixture of N-(1′-ethylpropyl)-8-bromo-10-(bis(4-(2,4,4-trimethylpentane-2-yl)phenyl)amino-perylene-3,4-dicarboximide and N-(1′-ethylpropyl)-9-(bis(4-(2,4,4-trimethylpentane-2-yl)phenyl)amino-perylene-3,4-dicarboximide which was used directly for the next step.
- 150 mg of the mixture of N-(1′-ethylpropyl)-8-bromo-10-(bis(4-(2,4,4-trimethylpentane-2-yl)phenyl)amino-perylene-3,4-dicarboximide and N-(1′-ethylpropyl)-9-(bis-(4-(2,4,4-trimethylpentane-2-yl)phenyl)amino-perylene-3,4-dicarboximide, 65 mg of bis-(4-(2,4,4-trimethylpentane-2-yl)phenyl)-amine (0.165 mmol), 15 mg of sodium tert-butoxide (0.156 mmol), 21 mg of tris(dibenzylidenacetone)dipalladium(0) (0.023 mmol), and 10 mg of tri-tert-butylphosphine (0.050 mmol) were dissolved in 7 mL of dry toluene under argon and stirred at 80° C. overnight. The reaction mixture was purified via silica column chromatography with dichloromethane and petrol ether (2:1). Yield: 40 mg dark green solid compound C8.
- 1H NMR (700 MHz, CD2Cl2, 298 K) δ [ppm]: 8.43 (d, J=7.5, 1H), 8.30-8.25 (m, 2H), 8.14 (d, J=8.2, 1H), 7.99 (d, J=1.6, 1H), 7.82 (d, J=8.1, 1H), 7.62 (d, J=1.5, 1H), 7.21-7.15 (m, 5H), 7.11 (d, J=8.7, 4H), 6.87 (d, J=8.5, 4H), 6.71 (d, J=8.6, 4H), 5.00-4.89 (m, 1H), 2.18-2.10 (m, 2H), 1.83-1.76 (m, 2H), 1.67 (s, 4H), 1.63 (s, 4H), 1.29 (s, 12H), 1.27 (s, 12H), 0.80 (t, J=7.4, 6H), 0.70 (s, 18H), 0.66 (s, 18H).
- 13C NMR (126 MHz, CD2Cl2, 298 K) δ [ppm]: 147.3, 146.7, 146.6, 146.2, 144.6, 144.3, 137.5, 137.4, 133.6, 132.1, 130.7, 130.6, 129.0, 128.1, 127.0, 127.4, 127.0, 126.7, 125.5, 122.56, 122.42, 120.48, 120.39, 119.64, 115.26, 57.61, 57.48, 57.42, 38.79, 38.61, 32.86, 32.81, 32.16, 32.14, 31.0, 31.9, 30.3, 25.6, 11.7, 1.3.
- IR spectrum (ATR) λmax [cm−1]=2954, 2873, 1692, 1654, 1593, 1564, 1507, 1461, 1351, 1254, 1085, 1015, 805, 752.
- UV-Vis spectrum (CH2Cl2): max [nm] (ε[M−1 cm−1])=612 (18,891).
- High Resolution Mass (ESI): [M]+: calculated: 1173.8050. found: 1173.8015, discrepancy: −3.0 ppm. The triphenylamine moiety is losing an electron to form [M]+ as well as [M+H]+.
- Elemental analysis (C80H95N3O4): calculated: 82.65%; C, 8.24%; H, 3.61%; N, % S found: 81.66%; C, 8.62%; H, 3.68%; N, % S.
-
- 115 mg of N-(1′-ethylpropyl)-9,11-bis(bis(4-(2,4,4-trimethylpentane-2-yl)phenyl)amino) perylene-3,4-dicarboximide (0.097 mmol) were dissolved in 8 mL of 2-methyl-2-butanol and 4 mL of 1,4-dioxane. 219 mg of potassium hydroxide (3.92 mmol) were added, the reaction mixture desoxygenated and refluxed under argon overnight. The reaction mixture was poured into a ice water/acetic acid mixture (10:2). The precipitate was filtered, washed with water and after drying dissolved in dichloromethane. 1-2 mL of acetic acid were added and the solution was stirred for 1-2 days. After removal of the dichloromethane under reduced pressure, methanol was added. The precipitate was filtered and washed with methanol. The crude mixture was used directly for the next step. Yield (crude): 100 mg dark green solid (93%)
- 100 mg of 9,11-bis(bis(4-(2,4,4-trimethylpentane-2-yl)phenyl)amino)perylene-3,4-dicarboxy acid monoanhydride (0.094 mmol), 2 g of glycine (0.026 mol) and 3 g of imidazole (0.044 mol) were mixed in a Schlenk tube and stirred under argon at 140° C. overnight. After cooling down dilute hydrochloric acid was added. The brown precipitate was filtered and washed with water. The crude product was purified by column chromatography on silica gel with dichloromethane, THF, and acetic acid. Yield: 95 mg dark green solid (90%) of compound C9.
- 1H-NMR (500 MHz, THF, 298 K) δ [ppm]: 8.47 (s, 2H), 8.38-8.30 (m, 2H), 8.15 (d, J=1.7, 1H), 7.97 (d, J=8.1, 1H), 7.78 (d, J=1.7, 1H), 7.33-7.20 (m, 9H), 6.96 (d, J=8.4, 4H), 6.83 (d, J=8.5, 4H), 4.78 (s, 2H), 1.77 (d, J=18.4, 8H, partially overlaid by solvent signal), 1.38 (d, J=7.9, 24H), 0.78 (d, J=15.2, 36H).
- 13C-NMR (126 MHz, THF, 298 K) δ [ppm]: 163.7, 147.3, 147.0, 146.6, 145.2, 144.8, 138.0, 132.3, 131.8, 131.4, 131.0, 128.6, 128.4, 127.9, 127.6, 127.3, 126.3, 125.8, 123.7, 123.1, 122.0, 121.3, 121.1, 120.9, 58.0, 57.9, 39.2, 39.0, 33.3, 33.2, 32.5, 32.23.
- IR spectrum (ATR) λmax [cm−1]=2951, 2901, 2871, 1697, 1662, 1593, 1561, 1506, 1365, 1250, 1172, 1132, 1013, 821, 755.
- UV-Vis spectrum (CH2Cl2) λmax [nm] (ε[M−1 cm−1])=631 (20,194).
- High Resolution Mass (ESI) [M]+: calculated: 1161.7323. found: 1161.7336, discrepancy: 1.2 ppm. The triphenylamine moiety is losing an electron to form [M]+ as well as [M+H]+.
-
- 500 mg of N-(1′-ethylpropyl)-8,11-dichloro-perylene-3,4-dicarboximide (1.09 mmol), 960 mg of bis-(9,9-dimethylfluorene-2-yl)-amine (2.39 mmol), 1.42 g caesium carbonate (4.34 mmol), 198 mg of tris(dibenzylideneacetone)dipalladium(0) (0.216 mmol), and 271 mg of 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.436 mmol) were dissolved in 30 mL of anhydrous toluene in a Schlenk tube and stirred under argon at 100° C. for 16 h. Monofunctionalised (8-functionalised and 9-functionalised) and difunctionalised product (8,11-functionalised and 8,10-functionalised) was obtained.
- The reaction mixture was purified via gel permeation chromatography to separate mono- and difunctionalised product with chloroform and via column chromatography with dichloromethane.
- Yield: 50 mg brown solid (4%) of compound C10.
- 1H-NMR (700 MHz, THF, 298 K) δ [ppm]: 8.44-8.37 (m, 4H), 8.27 (d, J=8.0, 2H), 7.68 (t, J=8.5, 8H), 7.44-7.38 (m, 10H), 7.27 (t, J=7.4, 4H), 7.24-7.18 (m, 8H), 5.06-4.97 (m, 1H), 2.29-2.18 (m, 2H), 1.89-1.76 (m, 2H), 1.40 (s, 24H), 0.85 (t, J=7.4, 6H).
- UV-Vis spectrum (CH2Cl2) λmax [nm] (ε=M−1 cm−1)=486 (25,828), 563 (13,369).
- High Resolution Mass (ESI) [M]+: calculated: 1189.5546. found: 1189.5527, discrepancy: −1.6 ppm. The triphenylamine moiety is losing an electron to form [M]+ as well as [M+H]+.
- The compound N-(1′-Ethylpropyl)8-(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)perylene-3,4-dicarboximide
- (also according to general formula III of the present invention) was obtained as by-product and characterized as follows.
- Yield: 115 mg brownish-red solid (14%).
- 1H-NMR (300 MHz, CD2Cl2, 298 K) δ [ppm]: 8.48 (d, J=8.0, 1H), 8.42 (d, J=2.1, 1H), 8.38-8.30 (m, 2H), 8.22 (d, J=7.1, 1H), 8.06 (d, J=8.2, 1H), 7.77-7.67 (m, 4H), 7.62 (d, J=8.0, 1H), 7.57 (d, J=1.9, 1H), 7.50 (d, J=7.7, 1H), 7.48-7.40 (m, 4H), 7.39-7.22 (m, 6H), 5.11-4.95 (m, 1H), 2.33-2.15 (m, 2H), 1.97-1.83 (m, 2H), 1.45 (s, 12H), 0.89 (t, J=7.5, 6H).
- UV-Vis spectrum (CH2Cl2) λmax [nm] (ε=M−1 cm−1])=477 (23,629).
- High Resolution Mass (ESI) [M]+: calculated: 790.3559. found: 790.3535, discrepancy: −3.1 ppm. The triphenylamine moiety is losing an electron to form [M]+ as well as [M+H]+.
-
- 50 mg of N-(1′-ethylpropyl)-8,11-bis(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)perylene-3,4-dicarboximide (0.042 mmol) were dissolved in 4 mL of 2-methyl-2-butanol and 2 mL of 1,4-dioxane. 95 mg of potassium hydroxide (1.68 mmol) were added, the reaction mixture deoxygenated and reuxed under argon overnight. The reaction mixture was poured into a ice water/acetic acid mixture (10:2). The precipitate was filtered, washed with water and after drying dissolved in dichloromethane. 1-2 mL of acetic acid were added and the solution was stirred for 1-2 days. After removal of the dichloromethane under reduced pressure, methanol was added. The precipitate was filtered and washed with methanol. The crude mixture was used directly for the next step. Yield (crude): 45 mg red solid (94%)
- 45 mg of 8,11-bis(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)perylene-3,4-dicarboxylic acid monoanhydride (0.036 mmol), 1 g of glycine (0.013 mol) and 2 g of imidazole (0.029 mol) were mixed in a Schlenk tube and stirred under argon at 140° C. overnight.
- After cooling down dilute hydrochloric acid was added. The brown precipitate was filtered and washed with water. The crude product was purified by column chromatography on silica gel with dichloromethane, THF, and acetic acid. Yield: 40 mg red solid (85%) of compound C11.
- 1H-NMR (300 MHz, THF, 298 K) δ [ppm]: 8.35-8.26 (m, 4H), 8.18 (d, J=8.2, 2H), 7.61-7.53 (m, 8H), 7.33-7.26, (m, 10H), 7.19-7.06 (m, 12H), 4.68 (s, 2H), 1.29 (s, 24H).
- 13C-NMR (176 MHz, THF, 298 K) δ [ppm]: 169.8, 164.0, 156.6, 154.9, 148.9, 148.4, 140.2, 139.0, 137.9, 136.4, 132.5, 131.5, 131.2, 128.2, 128.1, 127.9, 124.8, 123.7, 123.1, 122.5, 122.3, 122.1, 122.0, 121.0, 120.7, 120.3, 48.1, 27.7, 26.2, 26.1.
- UV-Vis spectrum (CH2Cl2) λmax [nm] (ε[M−1 cm−1])=477 (24,517), 574 (11,904).
- IR spectrum (ATR) λmax [cm−1]=3040, 2956, 2924, 2860, 1693, 1656, 1590, 1486, 1448, 1368, 1298, 1249, 1135, 1080, 1015, 966, 824, 777, 755, 734.
- High Resolution Mass (ESI) [M]+: calculated: 1177.4819. found: 1177.4797, discrepancy: −1.8 ppm. The triphenylamine moiety is losing an electron to form [M]+ as well as [M+H]+.
-
- 96 mg of N-(1′-ethylpropyl)-8-(bis(9,9-dimethyl-9H-fluoren-2-yl)amino)perylene-3,4-dicarboximide (0.122 mmol) were dissolved in 6 mL of 2-methyl-2-butanol and 3 mL of 1,4-dioxane. 255 mg of potassium hydroxide (4.55 mmol) were added, the reaction mixture deoxygenated and refluxed under argon overnight. The reaction mixture was poured into an ice water/acetic acid mixture (10:2). The precipitate was filtered, washed with water and after drying dissolved in dichloromethane. 1-2 mL of acetic acid were added and the solution was stirred for 1-2 days. After removal of the dichloromethane under reduced pressure, methanol was added. The precipitate was filtered and washed with methanol. The crude mixture was used directly for the next step. Yield (crude): 85 mg red solid (96%).
- 85 mg of 8-(bis(9,9-dimethyl-9H-uoren-2-yl)amino)perylene-3,4-dicarboxy monoanhydride (0.036 mmol), 1 g of glycine (0.013 mol) and 2 g of imidazole (0.029 mol) were mixed in a Schlenk tube and stirred under argon at 140° C. overnight. After cooling down dilute hydrochloric acid was added. The precipitate was filtered and washed with water. The crude product was purified by column chromatography on silica gel with dichloromethane, THF, and acetic acid.
- Yield: 80 mg red solid (87%) of compound C12.
- 1H-NMR (300 MHz, THF, 298 K) δ [ppm]: 8.66-8.39 (m, 5H), 8.29 (d, J=8.2, 1H), 7.77-7.68 (m, 5H), 7.61 (d, J=1.8, 1H), 7.56 (t, J=7.9, 1H), 7.49-7.39 (m, 4H), 7.34-7.18 (m, 6H), 4.81 (s, 2H), 1.43 (s, 12H).
- 13C-NMR (126 MHz, C2Cl4D2, 393 K) δ [ppm]: 155.6, 153.8, 146.6, 138.6, 137.8, 135.3, 131.7, 129.9, 127.4, 126.9, 126.8, 123.7, 122.3, 122.1, 121.7, 120.9, 120.8, 120.2, 120.2, 119.5, 119.1, 46.8, 40.5, 26.9.
- UV-Vis spectrum (CH2Cl2) λmax [nm] (ε[M−1 cm−1])=484 (26,991).
- IR spectrum (ATR) λmax [cm−1]=3630, 3499, 3058, 2957, 2923, 2860, 1750, 1691, 1651, 1591, 1570, 1448, 1407, 1370, 1292, 1247, 1172, 1073, 1020, 970, 853, 799, 755, 736.
- High Resolution Mass (ESI) [M]+: calculated: 778.2832. found: 778.2836, discrepancy: 0.6 ppm. The triphenylamine moiety is losing an electron to form [M]+ as well as [M+H]+.
-
- N-(1-heptyloctyl)-8,11-bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-y]-perylene-3,4-dicarboxylic acid (0.070 g, 0.09 mmol) and 1-bromo-2-nitrobenzene (0.054 g, 0.27 mmol) were mixed together and dissolved in 15 mL toluene and 0.15 mL ethanol. Potassium carbonate (148 mg, 1.07 mmol) was dissolved in 1.5 mL of water and added to the reaction mixture. After deoxygenation for 30 minutes, Pd(PPh3)4 (28 mg, 18 μmol) was added and the reaction mixture heated under argon atmosphere for 28 hours at 80° C. After cooling the reaction mixture to room temperature, the solvent was evaporated. The reaction mixture was dissolved in dichloromethane and filtered over silica. Finally the desired compound was obtained after gel permeation chromatography (BioBeads, THF). Yield: 82% (57 mg, 0.07 mmol) of compound C13.
- 1H NMR (250 MHz, Methylene Chloride-d2) δ 8.46 (s, 2H), 8.44-8.29 (m, 4H), 8.04 (dt, J=8.1, 1.8 Hz, 2H), 7.86 (t, J=1.8 Hz, 2H), 7.83-7.73 (m, 2H), 7.73-7.58 (m, 4H), 5.15 (tt, J=9.1, 5.8 Hz, 1H), 2.34-2.12 (m, 1H), 1.94-1.74 (m, 2H), 1.38-1.11 (m, 20H), 0.82 (t, J=6.4 Hz, 6H).
- 13C NMR (63 MHz, CD2Cl2) δ 149.50, 138.01, 136.38, 136.04, 134.82, 133.57, 132.88, 132.12, 131.37, 130.45, 130.35, 129.90, 129.70, 127.35, 127.26, 125.10, 124.33, 121.40, 54.78, 32.93, 32.38, 30.10, 29.80, 27.53, 23.18, 14.39.
- FD Mass Spectrum (8 kV): m/z=773.9 (100%) [M+]
- UV-vis (in CH2Cl2): λmax (ε[M−1 cm−1]): 476 nm (3.81×104 M−1 cm−1), 501 nm (4.20×104 M−1 cm−1).
- Elemental Analysis: calculated: 76.05% C; 6.12% H; 5.43% N; experimental (%): 75.58% C; 6.41% H; 5.30% N.
- Preparation of the (solid-state) DSCs: A TiO2 blocking layer was prepared on a fluorine-doped tin oxide (FTO)-covered glass substrate using spray pyrolysis (cf. B. Peng, G. Jungmann, C. Jager, D. Haarer, H. W. Schmidt, M. Thelakkat, Coord. Chem. Rev. 2004, 248, 1479). Next, a TiO2 paste (Dyesol), diluted with terpineol, was applied by screen printing, resulting in a film thickness of 1.7 μm. All films were then sintered for 45 min at 450° C., followed by treatment in a 40 mM aqueous solution of TiCl4 at 60° C. for 30 min, followed by another sintering step. The prepared samples with TiO2 layers were pretreated with 5 mM solutions of the additive 2-(p-butoxyphenyl)acetohydroxamic acid sodium salt in ethanol (this additive is described on page 52 of WO 2012/001628 A1 as “Example No. 6”). The electrodes were then dyed in 0.5 mM dye solution in CH2Cl2. Spiro-MeOTAD was applied by spin-coating from a solution in DCM (200 mg/mL) also containing 20 mM Li(CF3SO2)2N. Fabrication of the device was completed by evaporation of 200 nm of silver as the counter electrode. The active area of the sDSC was defined by the size of these contacts (0.13 cm2), and the cells were masked by an aperture of the same area for measurements. The current-voltage characteristics for all cells were measured with a Keithley 2400 under 1000 W/m2, AM 1.5G conditions (LOT ORIEL 450 W).
- The incident photon to current conversion efficiency's (IPCE) were obtained with an Acton Research Monochromator using additional white background light illumination. The samples were illuminated with monochromatic light from the quartz monochromator with deuterium lamp. The power of the incident light beam was (2-5). 10-8 W. The negative voltage of −300 V was supplied to the sample substrate. The counter-electrode with the 4.5×15 mm2 slit for illumination was placed at 8 mm distance from the sample surface. The counter-electrode was connected to the input of the BK2-16 type electrometer, working in the open input regime, for the photocurrent measurement. The 10−15-10−12 A strong photocurrent was flowing in the circuit under illumination. The photocurrent J is strongly dependent on the incident light photon energy hν. The J0.5=f(hν) dependence was plotted. Usually the dependence of the photocurrent on incident light quanta energy is well described by linear relationship between J0.5 and hν near the threshold (cf. E. Miyamoto, Y. Yamaguchi, M. Yokoyama, Electrophotography 1989, 28, 364 and M. Cordona, L. Ley, Top. Appl. Phys. 1978, 26, 1). The linear part of this dependence was extrapolated to the hν axis and Jp value was determined as the photon energy at the interception point.
- The results of the DSCs with varying dyes/compounds are given in the following table 1.
-
TABLE 1 Photovoltaic performance of DSCs based on the compounds C9, C11 and C12 EQEmax VOC ISC FF η Dye [%] [mV] [mAcm−2] [%] [%] C9 34 800 −5.82 71 3.3 C11 22 580 −1.59 55 0.5 C12 50 740 −4.63 60 2.1
Claims (7)
1-12. (canceled)
13. A process for the preparation of compounds of general formula IV
wherein the variables have the following meaning
R13, R14 independently of each other aryl or hetaryl,
m 0 or 1, where in the case of in equal 1 R14 is bound either to the 8 or 9 position of the perylene skeleton,
R3 identical or different radicals hydrogen, alkyl, cycloalkyl, aryl, hetaryl, alkoxy, aryloxy, arylthio, hetaryloxy, hetarylthio, diarylamino or dialkylamino,
n 0, 1, 2, 3 or 4
Y oxygen or NR12,
and
R2 hydrogen, alkyl, cycloalkyl, aryl or hetaryl,
or
a moiety of formula —Z-A, wherein
A is —COOM, —SO3M or —PO3M,
M hydrogen, alkali metal cation or [NR′]4+,
R′ hydrogen or alkyl, where the radicals R′ may be identical or different,
Z C1-C6-alkylene or 1,4-phenylene, where the phenylene radical may be substituted by one or more substituents alkyl, nitro, cyano and/or halogen,
comprising
reacting a compound of general formula I
m 0 or 1, where in the case of m equal 1 E2 is bound either to the 8 or 9 position of the perylene skeleton and is identical to E1,
W a bridging C2 or C3 moiety which may be substituted by one or more alkyl,
and the remaining variables R3, n and Y have the meaning as defined above with compounds of general formula Lg-R13 and Lg-R14 in the presence of a palladium containing catalyst under the conditions of the Suzuki coupling reaction.
14. A process according to claim 13 wherein in general formula IV the variables have the following meaning
R13, R14 independently of each other moieties of formulae IVa or IVb
15. A process according to claim 13 wherein in general formula IV
Lg chlorine, bromine, iodine, brosylate, nosylate, tosylate, mesylate or triflate.
16. Compounds of general formula IV according to claim 13 .
17. A method of preparing a dye-sensitized solar cell comprising dying an electrode with compounds of general formula IV prepared according to claim 13 .
18. A dye-sensitized solar cell comprising compounds of general formula IV prepared according to claim 13 .
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US13/958,934 US8816081B2 (en) | 2012-08-06 | 2013-08-05 | Boron containing perylene monoimides, a process for their production, their use as building blocks for the production of perylene monoimide derivatives, monoimide derivatives and their use in dye-sensitized solar cells |
US14/336,580 US9105410B2 (en) | 2012-08-06 | 2014-07-21 | Boron containing perylene monoimides, a process for their production, their use as building blocks for the production of perylene monoimide derivatives, monoimide derivatives and their use in dye-sensitized solar cells |
US14/746,113 US9624375B2 (en) | 2012-08-06 | 2015-06-22 | Boron containing perylene monoimides, a process for their production, their use as building blocks for the production of perylene monoimide derivatives, monoimide derivatives and their use in dye-sensitized solar cells |
US15/451,946 US20170178823A1 (en) | 2012-08-06 | 2017-03-07 | Boron containing perylene monoimides, a process for their production, their use as building blocks for the production of perylene monoimide derivatives, monoimide derivatives and their use in dye-sensitized solar cells |
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US14/336,580 Expired - Fee Related US9105410B2 (en) | 2012-08-06 | 2014-07-21 | Boron containing perylene monoimides, a process for their production, their use as building blocks for the production of perylene monoimide derivatives, monoimide derivatives and their use in dye-sensitized solar cells |
US14/746,113 Expired - Fee Related US9624375B2 (en) | 2012-08-06 | 2015-06-22 | Boron containing perylene monoimides, a process for their production, their use as building blocks for the production of perylene monoimide derivatives, monoimide derivatives and their use in dye-sensitized solar cells |
US15/451,946 Abandoned US20170178823A1 (en) | 2012-08-06 | 2017-03-07 | Boron containing perylene monoimides, a process for their production, their use as building blocks for the production of perylene monoimide derivatives, monoimide derivatives and their use in dye-sensitized solar cells |
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KR20160038052A (en) | 2013-08-05 | 2016-04-06 | 바스프 에스이 | Cyanated naphthalenebenzimidazole compounds |
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DE4236885A1 (en) * | 1992-10-31 | 1994-05-05 | Basf Ag | Quaterrylenetetracarboximides |
JP3968809B2 (en) | 1996-12-19 | 2007-08-29 | 富士ゼロックス株式会社 | Photo-semiconductor electrode for wet solar cell, wet solar cell, and photoelectric conversion method |
JP3968819B2 (en) | 1997-06-02 | 2007-08-29 | 富士ゼロックス株式会社 | Photo-semiconductor electrode for wet solar cell, wet solar cell, and photoelectric conversion method |
JP2000100484A (en) | 1998-09-24 | 2000-04-07 | Fuji Xerox Co Ltd | Light semiconductor electrode, photoelectric conversion device and photoelectric conversion method |
JP4211120B2 (en) | 1999-02-19 | 2009-01-21 | 富士ゼロックス株式会社 | Photo-semiconductor electrode, photoelectric conversion device, and photoelectric conversion method |
JP2001093589A (en) | 1999-09-21 | 2001-04-06 | Fuji Xerox Co Ltd | Optical semiconductor electrode, photoelectric conversion device and photoelectric conversion method |
EP1176646A1 (en) | 2000-07-28 | 2002-01-30 | Ecole Polytechnique Féderale de Lausanne (EPFL) | Solid state heterojunction and solid state sensitized photovoltaic cell |
DE102004054303A1 (en) | 2004-11-09 | 2006-05-11 | Basf Ag | Process for the preparation of perylene-3,4-dicarboxylic acid imides |
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US8471020B2 (en) * | 2011-03-03 | 2013-06-25 | Basf Se | Perylene-based semiconducting materials |
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US8481736B2 (en) * | 2006-04-07 | 2013-07-09 | Basf Se | Liquid crystalline rylene tetracarboxylic acid derivatives and use thereof |
US9054325B2 (en) * | 2012-02-09 | 2015-06-09 | 03;Basf Se | Rylene monoimide derivatives and use thereof as photosensitizers in solar cells and photodetectors |
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