WO2010012710A1 - Perylene tetracarboximide derivatives for photovoltaic devices - Google Patents
Perylene tetracarboximide derivatives for photovoltaic devices Download PDFInfo
- Publication number
- WO2010012710A1 WO2010012710A1 PCT/EP2009/059711 EP2009059711W WO2010012710A1 WO 2010012710 A1 WO2010012710 A1 WO 2010012710A1 EP 2009059711 W EP2009059711 W EP 2009059711W WO 2010012710 A1 WO2010012710 A1 WO 2010012710A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mmol
- perylene
- branched
- reaction mixture
- straight
- Prior art date
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- 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 description 19
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 title description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- -1 diisopropyl phenyl Chemical group 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 150000001345 alkine derivatives Chemical class 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 6
- 125000002950 monocyclic group Chemical group 0.000 claims description 4
- 125000003367 polycyclic group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 66
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 62
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 60
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 58
- 239000011541 reaction mixture Substances 0.000 description 51
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 48
- 239000000243 solution Substances 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 29
- 238000003786 synthesis reaction Methods 0.000 description 29
- 239000000203 mixture Substances 0.000 description 27
- 239000002904 solvent Substances 0.000 description 27
- 238000005160 1H NMR spectroscopy Methods 0.000 description 26
- 239000000047 product Substances 0.000 description 25
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 24
- 239000007787 solid Substances 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 238000013086 organic photovoltaic Methods 0.000 description 19
- 239000010410 layer Substances 0.000 description 18
- 238000002390 rotary evaporation Methods 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000000284 extract Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000000741 silica gel Substances 0.000 description 15
- 229910002027 silica gel Inorganic materials 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 12
- 235000019341 magnesium sulphate Nutrition 0.000 description 12
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 description 12
- 238000010791 quenching Methods 0.000 description 11
- 230000000171 quenching effect Effects 0.000 description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- 229910052741 iridium Inorganic materials 0.000 description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 10
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 235000015320 potassium carbonate Nutrition 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 6
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 6
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 6
- RNVFYQUEEMZKLR-UHFFFAOYSA-N methyl 3,5-dihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=CC(O)=C1 RNVFYQUEEMZKLR-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- YFTHTJAPODJVSL-UHFFFAOYSA-N 2-(1-benzothiophen-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(SC=C2)C2=C1 YFTHTJAPODJVSL-UHFFFAOYSA-N 0.000 description 5
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 5
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 4
- PLTWYBSYQRKPQG-UHFFFAOYSA-N C=1C=CSC=1C1(Br)CC=CS1.C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 Chemical compound C=1C=CSC=1C1(Br)CC=CS1.C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 PLTWYBSYQRKPQG-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000006399 behavior Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- CNLSKHCVAUZKTB-UHFFFAOYSA-N 3,5-didodecoxybenzoic acid Chemical compound CCCCCCCCCCCCOC1=CC(OCCCCCCCCCCCC)=CC(C(O)=O)=C1 CNLSKHCVAUZKTB-UHFFFAOYSA-N 0.000 description 3
- VDNOMEBXKZREHO-UHFFFAOYSA-N 6-iminohexyl 3,5-didodecoxybenzoate Chemical compound CCCCCCCCCCCCOC1=CC(OCCCCCCCCCCCC)=CC(C(=O)OCCCCCC=N)=C1 VDNOMEBXKZREHO-UHFFFAOYSA-N 0.000 description 3
- PONZBUKBFVIXOD-UHFFFAOYSA-N 9,10-dicarbamoylperylene-3,4-dicarboxylic acid Chemical class C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=N)C2=C1C3=CC=C2C(=N)O PONZBUKBFVIXOD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004776 molecular orbital Methods 0.000 description 3
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 2
- KXSFECAJUBPPFE-UHFFFAOYSA-N 2,2':5',2''-terthiophene Chemical compound C1=CSC(C=2SC(=CC=2)C=2SC=CC=2)=C1 KXSFECAJUBPPFE-UHFFFAOYSA-N 0.000 description 2
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 2
- GNUQBBPWNRAMGC-UHFFFAOYSA-N 2-(2-hexyl-3h-thiophen-2-yl)-3-thiophen-2-ylthiophene Chemical compound S1C=CC(C=2SC=CC=2)=C1C1(CCCCCC)CC=CS1 GNUQBBPWNRAMGC-UHFFFAOYSA-N 0.000 description 2
- KHOSPPAIKYQCQD-UHFFFAOYSA-N 2-(2-hexyl-3h-thiophen-2-yl)thiophene Chemical compound C=1C=CSC=1C1(CCCCCC)CC=CS1 KHOSPPAIKYQCQD-UHFFFAOYSA-N 0.000 description 2
- QZVHYFUVMQIGGM-UHFFFAOYSA-N 2-Hexylthiophene Chemical compound CCCCCCC1=CC=CS1 QZVHYFUVMQIGGM-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- QBGPSEDSHFOKJR-UHFFFAOYSA-N boric acid;2-(2-hexyl-3h-thiophen-2-yl)-3-thiophen-2-ylthiophene Chemical compound OB(O)O.S1C=CC(C=2SC=CC=2)=C1C1(CCCCCC)CC=CS1 QBGPSEDSHFOKJR-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- BBNGOPAHRDCHNZ-UHFFFAOYSA-N methyl 3,5-didodecoxybenzoate Chemical compound CCCCCCCCCCCCOC1=CC(OCCCCCCCCCCCC)=CC(C(=O)OC)=C1 BBNGOPAHRDCHNZ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- ARYHTUPFQTUBBG-UHFFFAOYSA-N thiophen-2-ylboronic acid Chemical compound OB(O)C1=CC=CS1 ARYHTUPFQTUBBG-UHFFFAOYSA-N 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- KGCJCDXZSPVGGX-UHFFFAOYSA-N 1-bromoperylene Chemical group C1=CC(C=2C(Br)=CC=C3C=2C2=CC=C3)=C3C2=CC=CC3=C1 KGCJCDXZSPVGGX-UHFFFAOYSA-N 0.000 description 1
- UPOXMRITEFEFOG-UHFFFAOYSA-N 2,3-dithiophen-2-ylthiophene perylene Chemical compound C1=CSC(C2=C(SC=C2)C=2SC=CC=2)=C1.C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 UPOXMRITEFEFOG-UHFFFAOYSA-N 0.000 description 1
- HVKXVCDUSKRXKX-UHFFFAOYSA-N 2-(2-bromo-3H-thiophen-2-yl)-3-thiophen-2-ylthiophene perylene Chemical compound S1C=CC(C=2SC=CC=2)=C1C1(Br)CC=CS1.C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 HVKXVCDUSKRXKX-UHFFFAOYSA-N 0.000 description 1
- LSIYDKGTGHFTFW-UHFFFAOYSA-N 2-bromo-5-hexylthiophene Chemical compound CCCCCCC1=CC=C(Br)S1 LSIYDKGTGHFTFW-UHFFFAOYSA-N 0.000 description 1
- KUJYDIFFRDAYDH-UHFFFAOYSA-N 2-thiophen-2-yl-5-[5-[5-(5-thiophen-2-ylthiophen-2-yl)thiophen-2-yl]thiophen-2-yl]thiophene Chemical group C1=CSC(C=2SC(=CC=2)C=2SC(=CC=2)C=2SC(=CC=2)C=2SC(=CC=2)C=2SC=CC=2)=C1 KUJYDIFFRDAYDH-UHFFFAOYSA-N 0.000 description 1
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- IMXNSYLJKARJKD-UHFFFAOYSA-N 6-[(2-bromoperylen-1-yl)amino]hexan-1-ol Chemical group C1=CC(C=2C(NCCCCCCO)=C(Br)C=C3C=2C2=CC=C3)=C3C2=CC=CC3=C1 IMXNSYLJKARJKD-UHFFFAOYSA-N 0.000 description 1
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- AYVQDNKHPMWPMQ-UHFFFAOYSA-N B(O)(O)O.C(CCCCC)C1=C(SC=C1)C=1SC=CC1C=1SC=CC1 Chemical compound B(O)(O)O.C(CCCCC)C1=C(SC=C1)C=1SC=CC1C=1SC=CC1 AYVQDNKHPMWPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000002618 bicyclic heterocycle group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- NEWMXKLTJWYHKG-UHFFFAOYSA-N boric acid;2-(2-hexyl-3h-thiophen-2-yl)thiophene Chemical compound OB(O)O.C=1C=CSC=1C1(CCCCCC)CC=CS1 NEWMXKLTJWYHKG-UHFFFAOYSA-N 0.000 description 1
- NMFFQIWOMOZFSU-UHFFFAOYSA-N boric acid;3-hexyl-2-thiophen-2-ylthiophene Chemical compound OB(O)O.C1=CSC(C=2SC=CC=2)=C1CCCCCC NMFFQIWOMOZFSU-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZBQUMMFUJLOTQC-UHFFFAOYSA-L dichloronickel;3-diphenylphosphanylpropyl(diphenyl)phosphane Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 ZBQUMMFUJLOTQC-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HKNRNTYTYUWGLN-UHFFFAOYSA-N dithieno[3,2-a:2',3'-d]thiophene Chemical compound C1=CSC2=C1SC1=C2C=CS1 HKNRNTYTYUWGLN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005446 heptyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- 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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
-
- 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 to perylene tetracarboximide derivatives.
- the present invention further relates to oligothiophene-conjugated perylene tetracarboximides (TCPTCDI) and the use thereof in photovoltaic devices.
- TCPCDI oligothiophene-conjugated perylene tetracarboximides
- Photovoltaic devices are used to convert light into electrical energy. Photovoltaic devices are characterized by their efficiency with which they can convert incidental light to useful electrical energy.
- photovoltaic devices have been made of various inorganic semiconductors, e.g., crystalline, polycrystalline, and amorphous silicon, gallium arsenide, cadmium telluride, and others.
- Devices utilizing crystalline or amorphous silicon dominate commercial applications, and some have achieved high efficiencies.
- high efficiency amorphous silicon devices have problems with stability.
- organic photovoltaic (OPV) devices are being researched and developed to achieve acceptable photovoltaic conversion efficiencies with economical production costs.
- OPO organic photovoltaic
- hetrojunction OPV dispersed heterojunction OPV with a donor- acceptor system, consisting of n- and p-type conducting materials in a double layers separately (hetrojunction OPV) or a single layer prepared by blending the two n- and p- type materials (dispersed heterojunction OPV).
- hetrojunction OPV n- and p-type conducting materials in a double layers separately
- dispensersed heterojunction OPV dispersed heterojunction OPV
- the success and efficiency of dispersed hetrojunction OPV is largely depend on the domain size of interpenetrating donor-acceptor network whose size is ideally in the range of 10 nm.
- controlling the morphology of the organic compound in dispersed heterojunction devices is critical.
- One way of controlling the morphology of an organic compound is to produce a molecular heterojunction by covalently linking electron-donor and acceptor molecules. Due to their unique optical and electrical properties, molecular heterojunction materials, i.e., donor-acceptor linked molecules, are likely to have important applications in OPV devices and, thus, have triggered intense scientific research.
- oligothiophene and perylene tetracarboximide functional units have been extensively studied since the former preserves its typical charge-transport and self-assembling properties, while the latter provides high molar absorptivity in the visible region as well as electron- accepting properties.
- Cremer et al "Perylene-Oligothiophene- Perylene Triads for Photovoltaic Applications," Eur. J. Org.
- Chem., 3715-3723 (2005) discloses acceptor-donor-acceptor triad systems consisting of head-to- tail-coupled oligo(3-hexylthiophenes) integrated between two terminal perylenemonoimides which can be used for organic solar cells.
- acceptor-donor-acceptor triad systems consisting of head-to- tail-coupled oligo(3-hexylthiophenes) integrated between two terminal perylenemonoimides which can be used for organic solar cells.
- Chen et al. “Oligothiophene-Functionalized Perylene Bisimide System: Synthesis, Characterization, and Electrochemical Polymerization Properties, " Chem. Mater., 17:2208-2215 (2005) describes perylene bisimides derivatives functionalized with two oligothiophene substituents.
- Xiaowei et al. "A High-Mobility Electron-Transport Polymer with Broad Absorption and Its Use in Field-Effect Transistors and All-Polymer Solar Cells," J. Am. Chem. Soc. 129:7246-7247 (2007) discloses a copolymer of perylene diimide and dithienothiophene building blocks exhibiting broad absorption ranging from the visible to the near infrared regions.
- Huang et al. "Size Effects of Oligothiphene on the Dynamics of Electron Transfer in ⁇ -Conjugated Oligothiophene-Perylene Bisimide Dyads," J. Phys. Chem.
- Figures la-e are cyclic vo Mammograms of the TCPTCDIs of the present invention.
- Figure 2 and 3 are energy band diagrams of the TCPTCDIs of the present invention and other OPV materials.
- Figure 4 is a band diagram of an ideal electron donor for fullerene derivative [6,6]-phenyl-C6i-butyric acid methyl ester (PCBM).
- Figures 5a-b are UV-vis absorption spectra of the TCPTCDIs of the present invention.
- FIG. 6 shows the thermogravimetric analysis (TGA) curves of the TCPTCDIs of the present invention.
- Figure 7 compares the UV-vis absorption spectra of the TCPTCDI of the present invention and the iridium complex.
- Figure 8 shows the phosphorescent quenching spectra of an iridium complex by the TCPTCDIs of the present invention.
- FIG. 9 is a Stern- Vo lmer plot of the quenching of an iridium complex by the TCPTCDIs of the present invention.
- the present invention relates to oligothiophene-conjugated perylene tetracarboximide (TCPTCDI) derivatives and the use thereof, as well as molecular heterojunction materials comprising the same for OPV devices.
- the TCPTCDI derivatives of the present invention may act as electron donor, acceptor, or donor-acceptor linked molecules in OPV devices.
- the TCPTCDI derivatives of the present invention can be represented by formula (I): wherein:
- R 1 , R 2 , R3, R 4 , R5, R 6 , R7, R8, Rio, Rn, X 1 , X 2 , and X3 are the same or different at each occurrence and are selected from the group consisting of -H, -F, -Cl, -Br, - NO 2 , -CN, a straight or branched Ci_2o alkyl, a C2-20 alkene, a C2-20 alkyne, a C3_2o cyclic alkyl, a straight or branched Ci_2o alkoxy, a Ci_2o dialkylamino, a C4_2o polyoxaalkyl, a C4_2o polythioalkyl, a C4_2o polyazaalkyl, a C4_i4 aryl, and a C 4-14 heteroaryl which may be substituted with one or more non-aromatic radicals, wherein Rio and Rn or any of Ri
- alkyl refers to hydrocarbon radicals containing preferably 1 to 20, more preferably 1 to 10, most preferably 1 to 6 carbon atoms. Specific examples thereof include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, and heptyl groups.
- alkene refers to hydrocarbon radicals having at least one double bond, containing preferably 2 to 20, more preferably 2 to 10, most preferably 2 to 6 carbon atoms.
- alkyne refers to hydrocarbon radicals having at least one triple bond, containing preferably 2 to 20, more preferably 2 to 10, most preferably 2 to 6 carbon atoms.
- alkoxy refers to an alkyl group containing preferably 1 to 20, more preferably 1 to 10, most preferably 1 to 6 carbon atoms, covalently bound to an oxygen atom. Specific examples thereof include, but are not limited to, methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, t-butoxy, pentyloxy, hexyloxy, and heptyloxy groups.
- cyclic alkyl refers to cyclic hydrocarbon radicals containing preferably 3 to 20, more preferably 3 to 10, most preferably 5 or 6 carbon atoms, which do not give steric hindrance. Specific examples thereof include, but are not limited to, cyclopentyl and cyclo hexyl groups.
- aryl refers to carbocyclic rings with a degree of unsaturation present so as to impart aromaticity to the ring. Specific examples thereof include, but are not limited to, phenyl, naphthyl, anthracenyl, biphenyl, pyrenyl, and perylene groups.
- heteroaryl refers to a substituted or unsubstituted heterocyclic aromatic ring, which can be a five-member ring heterocycle, a six-member ring heterocycle, or a ring-fused bicyclic heterocycle. Specific examples thereof include, but are not limited to, pyridyl, bipyridyl, acridyl, thiophene, imidazole, oxazole, thiazole, and quinolinyl groups.
- polyoxa-, polythio-, and polyaza- refers to hydrocarnon radicals containing more than two oxygen, sulphur, and nitrogen atoms in the chain.
- the perylene tetracarboximides of particular interest in the frame of the invention preferably have at least x or y which is not equal to zero and even more particularly, x+y which is equalt to or higher than 2.
- perylene tetracarboximides having ⁇ -conjugated oligothiophene groups are perylene tetracarboximides having ⁇ -conjugated oligothiophene groups.
- the electronic interactions between the perylene tetracarboximides and the thiophene units also increase.
- By changing the number of the thiophene repeating units it is possible to control the energy levels of high occupied molecular orbital (HOMO) and low unoccupied molecular orbital (LUMO) of the compounds.
- HOMO high occupied molecular orbital
- LUMO low unoccupied molecular orbital
- Ri is -H or a straight or branched Ci_2o alkyl which may be substituted with one or more non-aromatic radicals.
- Ri is -H or a C ⁇ alkyl.
- Ri is selected from a cyano or carboxyl group. Introducing electron- withdrawing cyano groups at the end of the oligothiophene units, while adding an extra olefm-conjugated moiety, might lower the energy levels (i.e., H0M0/LUM0) and allow smaller energy gap of the compound, leading to a better electron accepting ability. Further, the electron- withdrawing carboxyl group at the end might also make the compound useful as a light absorbing dye for dye-sensitized solar cells (DSSCs).
- Ri may be selected from the group consisting of a ⁇ nnd ⁇
- R 2 and R3 are C 4 -I 4 aryl which may be substituted with one or more non-aromatic radicals. More preferably, both R 2 and R3 are a 2,6- diisopropylphenyl group.
- all OfR 4 , R 5 , R ⁇ , and R 7 are -H.
- the photovoltaic performance was enhanced. It has been found that the solubility and self-assembling property of the compound can be improved by selecting an appropriate Rs.
- Rs is a straight or branched Ci_ 2 o alkyl which may be substituted with one or more substituent represented by the following formula: wherein Ri 2 is selected from the group consisting of -F, -Cl, -Br, -NO 2 , - CN, a straight or branched Ci_ 2 o alkyl, a C2-20 alkene, a C2-20 alkyne, a C3-20 cyclic alkyl, a straight or branched Ci_ 2 o alkoxy, a Ci_ 2 o dialkylamino, a C 4 _ 2 o polyoxaalkyl, a C 4 _ 2 o polythioalkyl, a C 4 _ 2 o polyazaalkyl, a C 4 _i 4 aryl, and a C 4 _i 4 heteroaryl which may be substituted with one or more non-aromatic radicals, wherein, when f is an integer of at
- the compounds of Formula II, where n is 2, 3, 4, 5, and 6, are designated as SP2TH, SP3TH, SP4TH, SP5TH, and SP6TH, respectively.
- n is an integer from 2 to 6.
- the compounds of Formula III, where n is 2, 3, 4, 5, and 6, are designated as SP2T, SP3T, SP4T, SP5T, and SP6T, respectively.
- the following scheme shows a synthetic pathway for a PTCDI derivative of the present invention.
- Perylene-3,4,9,10-tetra-carboxylic dianhydride (32 g, 81.4 mmol) was dissolved in 450 mL of 98% H 2 SO 4 and then 0.77 g (3.03 mmol) of iodine was added in the reaction mixture and stirred at room temperature (RT) for 2 h.
- the reaction temperature was set at 8O 0 C and then 9.2 mL (180 mmol) of bromine was added dropwise over 2 h.
- the reaction was conducted at the same temperature for 16 h.
- the reaction mixture was cooled to RT, and the excess Br 2 was displaced by purging with N 2 .
- the product was precipitated by an addition of ice water and collected by suction filtration. The precipitate was washed with water several times until the aqueous layer became neutral to yield dibromo- dianhydride as a crude product.
- the crude product was dried under reduced pressure at 12O 0 C.
- the crude dibromo compound (2.75 g, 5 mmol) was dissolved in 5 mL of acetic acid and 20 mL of N-methylpyrrolidone (NMP) was added.
- NMP N-methylpyrrolidone
- 2.21 g (12.5 mmol) of 2,6-diisopropylaniline was added into the reaction mixture and then the reaction mixture was refluxed for 120 h.
- the mixture was cooled down to RT and then poured onto crushed ice.
- the solid was filtered and washed with water and then dried in the oven for one day.
- the residue was purified by a column (silica gel, 5% ethyl acetate in n-hexane) to provide the product, diamino-diimide (37%) as an orange colored solid.
- Methyl 3,5-dihydroxybenzoate (4.2 g, 25 mmol) was dissolved in 25 mL of dry DMF and then 13.86 g (100 mmol) OfK 2 CO 3 was added in the reaction mixture, where the above mixture was stirred at 8O 0 C for 1 h under a N 2 atmosphere and then 1-bromododecane (12.4 g, 50 mmol) was added dropwise to the reaction mixture. The reaction mixture was stirred at 9O 0 C for 24 h under N 2 . At the end of the reaction, the mixture was poured onto ice, 2N-HC1 and extracted with MC, H 2 O, NaHCO 3 and brine. The solvent was removed in vacuo.
- Methyl 3,5-bis-dodecyloxybenzoate (8 g) was refluxed for 6 h with EtOH (25 rnL) and 10 % KOH . Then, the mixture was cooled and poured onto ice H 2 O and extracted with MC, then the organic layer was stored over dry MgSO 4 . The solvent was removed; the crude was recrystallized in EtOH to yield 85% of the benzoic acid product as a white solid.
- Bromo-6-hydroxyhexylaminoperylene bisimide (0.27 g, 0.3 mmol) was dissolved in 20 mL Of CH 2 Cl 2 and 3,5-bisdodecyloxybenzoic acid (0.2 g, 0.4 mmol), DCC (0.31g, 1.5 mmol), and DMAP (0.12 g, 1 mmol) were added.
- the reaction mixture was stirred at RT for 24 h under N 2 . At the end of the reaction, the mixture was poured into 2N-HC1 and then filtered. The organic layer was extracted with MC, washed with water and then the organic extract was stored over MgSO 4 .
- Gringard reagent 2-thiophenylmanesium bromide was prepared from 60 g of 2-bromothiophene (0.368 mole) and magnesium (9.7 g, 0.404 mole). Magnesium was slowly added to a mixture of 2-bromothiophene (50 g, 0.307 mole), Ni(dppp)Cl 2 (1.66 g, 3 mmol) in 150 mL dry ether at O 0 C. The mixture was warmed to RT for 20 h before being quenched by diluted HCl. The aqueous layer was extracted with ether and all organic layers were combined. The solvent was evaporated after drying over MgSO 4 .
- Bithiophene (5 g, 30 mmol) was dissolved in 100 niL of dry THF. The mixture is stirred at -78 0 C and n-BuLi (20.6 rnL, 33 mmol) is added to the reaction mixture. The reaction mixture was stirred at RT for 1 h. The 2- isopropoxy-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (6.7 g, 36 mmol) was added to the mixture at -78 0 C and then the resulting mixture was stirred at -78 0 C for 1 h and warmed to RT and stirred overnight. At the end of the reaction, the mixture was poured into water and extracted with ether and dried over MgSO 4 .
- the starting monobromo-substituted perylene bisimide ester (0.275 g, 0.2 mmol) was dissolved in 25 mL of dry THF.
- a solution of 2N K 2 CO 3 (3 mL) and 2 mol% (0.005 g) tetrakis(triphenylphosphine) palladium(O) were added into the reaction mixture, and then 0.117 g (0.4 mmol) of bithiophene borate was added.
- the resulting reaction mixture was refluxed for 24 h in N 2 before being poured into water and 2N-HC1.
- the aqueous layer was extracted with MC and the organic extracts were dried over magnesium sulfate.
- 2-Bromothiophene (1.63 g, 10 mmol) was dissolved in 25 rnL dry THF and a solution of 2N K 2 CO 3 (5 rnL) was added to the reaction mixture. And then 2 mol% (0.115 g) tetrakis(triphenylphosphine) palladium(O) and 2-hexyl-5- thiophene borate (2.94 g, 10 mmol) were added to the reaction mixture. The reaction mixture was refluxed for 24 h in N 2 . Before being poured into water and 2N-HC1, the aqueous layer was extracted with MC and the organic extracts were dried over magnesium sulfate.
- the starting monobromo-substituted perylene bisimide ester (0.275 g, 0.2 mmol) was dissolved in 25 rnL dry THF.
- a solution of 2N K2CO3 (3 mL) and 2 mol% (0.005 g) tetrakis(triphenylphosphine) palladium(O) were added to the reaction mixture and then 0.150 g (0.4 mmol) of 2-hexylbithiophene borate was added.
- the reaction mixture was refluxed for 24 h in N 2 before being poured into water and acidifying with 2N-HC1.
- the aqueous layer was extracted with MC and the organic extracts were dried over magnesium sulfate.
- the solvent was removed by rotary evaporation and the residue was purified by a column (silica gel, 20% EA and n-hexane) to yield 81% of the product as a green solid.
- the perylene bromobithiophene bisimide ester (0.77 g, 0.5 mmol) was dissolved in 25 niL dry THF.
- a solution of 2N K 2 CO 3 (3 mL) and 2 mol% (12 mg) tetrakis(triphenylphosphine) palladium(O) were added into the reaction mixture, and then thiopheneboronic acid (0.192 g, 1.5 mmol) was added.
- the reaction mixture was refluxed for 24 h under N 2 , before being poured into water and acidifying with 2N-HC1.
- the aqueous layer was extracted with MC and the organic extracts were dried over magnesium sulfate.
- 2-Bromo-5-hexylthiophene (1.22 g, 5 mmol) was dissolved in 25 mL dry THF.
- a solution of 2M K 2 CO 3 (5 mL) and 2 mol% (0.115 g) tetrakis(triphenylphosphine) palladium(O) were added into the reaction mixture and then bithiophene borate (1.46 g, 5 mmol) was added.
- the reaction mixture was refluxed for 24 h in N 2 before being poured into water and 2N-HC1.
- the aqueous layer was extracted with MC and the organic extracts were dried over magnesium sulfate.
- the bromo-perylene bisimide ester (1 g, 0.73 mmol) was dissolved in 25 rnL dry THF and a solution of 2N K2CO3 (3 rnL) was added into the reaction mixture. And then 2 mol% (12 mg) tetrakis(triphenylphosphine) palladium(O) and 2-hexylterthiophene borate (0.5 g, 1.08 mmol) were added into the reaction mixture.
- the reaction mixture was refluxed for 24 h in N 2 before being poured into water, and acidifying with 2N-HC1.
- the aqueous layer was extracted with MC and the organic extracts were dried over magnesium sulfate.
- the perylene 2-bromobithiophene bisimide ester (0.308 g, 0.2 mmol) was dissolved in 25 rnL dry THF and a solution of 2N K2CO3 (3 mL) was added into the reaction mixture. Then 2 mol% (0.005 g) tetrakis(triphenylphosphine) palladium(O) and 0.117 g (0.4 mmol) of bithiophene borate (0.117 g, 0.4 mmol)
- reaction mixture was refluxed for 24 h in N 2 before being poured into water, and acidifying with 2N-HC1.
- the aqueous layer was extracted with MC and the organic extracts were dried over magnesium sulfate.
- the solvent was removed by rotary evaporation and the residue was purified by a column (silica gel, 20% EA and n-hexane) to yield 50% of the product as a green solid.
- the perylene 2-bromobithiophene bisimide ester (0.308 g, 0.2 mmol) was dissolved in 25 rnL dry THF and a solution of 2N K2CO3 (3 mL) was added into the reaction mixture. Then 2 mol% (0.005 g) tetrakis(triphenylphosphine) palladium(O) and
- the perylene 2-bromobithiophene bisimide ester (0.308 g, 0.2 mmol) was dissolved in 25 mL dry THF and a solution of 2N K2CO3 (3 mL) was added into the reaction mixture. Then 2 mol% (0.005 g) tetrakis(triphenylphosphine) palladium(O) and terthiophene borate (0.15 g, 0.4 mmol) were added into the reaction mixture. The resulting reaction mixture was refluxed for 24 h in N 2 before being poured into water and acidifying with 2N-HC1. The aqueous layer was extracted with MC and the organic extracts were dried over magnesium sulfate.
- the perylene 2-bromobithiophene bisimide ester (0.308 g, 0.2 mmol) was dissolved in 25 mL dry THF and a solution of 2N K2CO3 (3 mL) was added into the reaction mixture. Then 2 mol% (0.005 g) tetrakis(triphenylphosphine) palladium(O) and hexylterthiophene borate (0.18 g, 0.4g) were added. The resulting reaction mixture was refluxed for 24 h in N 2 , before being poured into water and acidifying with 2N-HC1. The aqueous layer was extracted with MC and the organic extracts were dried over magnesium sulfate.
- Electrochemical measurements were performed by using a CHI600C (CH Instruments Inc., USA) with an electrochemical cell consisting of a platinum electrode (2 mm diameter), a Pt wire counter electrode, and a Ag/ AgCl reference electrode at RT.
- 0.1 M Tetrabutylammonium perchlorate (Bu 4 NClO 4 , TBAP) in dichloromethane (Aldrich, HPLC grade) was used as a supporting electrolyte (scan rate 5OmVs "1 ).
- Figures la-e show cyclic vo Mammograms of the TCPTCDIs of the present invention.
- the HOMO levels of SP2TH-SP6TH were determined as -5.35 eV, - 5.30 eV, -5.28 eV, -5.14 eV, and -5.13 eV, respectively.
- An increase in thiophene conjugation resulted in a slight increase in HOMO levels (0.22 eV).
- FIGS 2 and 3 show energy band diagrams of the TCPTCDIs synthesized in the above examples and other OPV materials.
- TCPTCDIs could be an electron donor toward C60, C70 and PCBM or an acceptor toward P3HT and iridium complex.
- the TCPTCDIs of the present invention could be used as an ideal electron donor for a PCBM acceptor.
- Reynolds et al. reported that the energy levels of an ideal electron donor for the PCBM acceptor should be -3.8 eV—5.2 eV (see, Reynolds et al, Macromolecules, 38:5359 (2005), Leclerc et al, J. Am. Chem. Soc. 130:732 (2008), and Scharber et al, J. Adv. Mater. 18: 789 (2006)).
- the oligothiophene- conjugated perylene tetracarboximide has a LUMO of -3.58 eV and a HOMO of -5.35 eV, which are almost identical to the values ideal for being a donor material for PCBM.
- Example 30 UV-vis Absorption Spectra The UV-vis absorption spectra of the compounds obtained in Examples 1-
- the SPT derivatives have similar or identical absorption behaviour as those of the SPTH derivatives, and the quarterthiophene-conjugated PTCDI has the strongest molar absorptivity. All oligothiophene-conjugated PTCDIs exhibit strong absorption bands up to the end of the visible region around 800 nm. Thus, they can be used as low band gap OPV materials.
- TGA Thermal gravimetric analysis
- DSC differential scanning calorimetric analysis
- TCPTCDIs may also be used as acceptor molecules when a donor molecule having a higher energy band than TCPTCDI is employed.
- Ir(btp)2(acac) or P3HT can be used as a donor molecule (see Figure 4).
- the quenching of triplet phosphorescence of the iridium complex Ir(btp)2(acac) was determined by using TCPTCDIs.
- FIG. 8 The phosphorescent quenching spectra of the Ir complex measured by varying the ratio of the Ir complex to SP2T is shown in Figure 8.
- Figure 9 is a Stern- Volmer plot of the quenching of the iridium complex by the TCPTCDIs.
- the quenching rate constant was calculated from the triplet lifetime (iridium complex) and the slope of the Stern- Volmer plot.
- the quenching rate constant using SP2T was calculated as 1.1 X 10 10 M 1 S 1 .
- Other quenching rate constants using TCPTCDIs are given in Table 3 below.
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CN200980129674.9A CN102112470B (en) | 2008-07-29 | 2009-07-28 | Perylene tetracarboximide derivatives for photovoltaic devices |
US13/055,939 US8618298B2 (en) | 2008-07-29 | 2009-07-28 | Perylene tetracarboximide derivatives for photovoltaic devices |
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JP2011254071A (en) * | 2010-05-07 | 2011-12-15 | Sumitomo Chemical Co Ltd | Organic photoelectric conversion element |
CN103080116A (en) * | 2010-09-10 | 2013-05-01 | 海洋王照明科技股份有限公司 | Perylenetetracarboxylic acid diimide organic semiconductive material, preparation method and use thereof |
WO2013180230A1 (en) | 2012-06-01 | 2013-12-05 | 三菱化学株式会社 | Method for producing metal oxide-containing semiconductor layer and electronic device |
WO2013180243A1 (en) | 2012-05-31 | 2013-12-05 | 三菱化学株式会社 | Copolymer, organic semiconductor material, organic electrical device, and solar cell module |
JP2014508741A (en) * | 2011-01-10 | 2014-04-10 | ビーエーエスエフ ソシエタス・ヨーロピア | Naphthalene diimide and lylene diimide compounds substituted with thiocyanate or isothiocyanate, and their use as n-type semiconductors |
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JP2014029905A (en) * | 2012-07-31 | 2014-02-13 | Fuji Electric Co Ltd | Method for manufacturing organic thin-film solar cell |
EP3126470B1 (en) * | 2014-03-31 | 2020-11-04 | Sony Corporation | Perylene-based materials for organic photoelectric conversion layers |
CN110467827B (en) * | 2019-08-09 | 2021-08-10 | 南京邮电大学 | Organic bulk heterojunction photovoltaic cell and preparation method thereof |
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JP2011254071A (en) * | 2010-05-07 | 2011-12-15 | Sumitomo Chemical Co Ltd | Organic photoelectric conversion element |
JP2015164217A (en) * | 2010-05-07 | 2015-09-10 | 住友化学株式会社 | organic photoelectric conversion element |
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EP2615097A1 (en) * | 2010-09-10 | 2013-07-17 | Ocean's King Lighting Science&Technology Co., Ltd. | Perylenetetracarboxylic acid diimide organic semiconductive material, preparation method and use thereof |
EP2615097A4 (en) * | 2010-09-10 | 2014-07-30 | Oceans King Lighting Science | Perylenetetracarboxylic acid diimide organic semiconductive material, preparation method and use thereof |
CN103080116B (en) * | 2010-09-10 | 2015-10-21 | 海洋王照明科技股份有限公司 | Yi Lei perylene tetracarboxylic acid diimides organic semiconductor material and its preparation method and application |
JP2014508741A (en) * | 2011-01-10 | 2014-04-10 | ビーエーエスエフ ソシエタス・ヨーロピア | Naphthalene diimide and lylene diimide compounds substituted with thiocyanate or isothiocyanate, and their use as n-type semiconductors |
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