CN107778319B - A-D-A type micromolecule compound containing hepta-fused ring structure indacene and preparation method thereof - Google Patents
A-D-A type micromolecule compound containing hepta-fused ring structure indacene and preparation method thereof Download PDFInfo
- Publication number
- CN107778319B CN107778319B CN201711077458.7A CN201711077458A CN107778319B CN 107778319 B CN107778319 B CN 107778319B CN 201711077458 A CN201711077458 A CN 201711077458A CN 107778319 B CN107778319 B CN 107778319B
- Authority
- CN
- China
- Prior art keywords
- carbon atoms
- hepta
- indacene
- compound containing
- group
- 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.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 33
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 150000002467 indacenes Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000013086 organic photovoltaic Methods 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- -1 small molecule compound Chemical class 0.000 claims 7
- 238000000034 method Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 12
- 230000003287 optical effect Effects 0.000 abstract description 5
- 229930192474 thiophene Natural products 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 34
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000010992 reflux Methods 0.000 description 13
- 239000000370 acceptor Substances 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229940126214 compound 3 Drugs 0.000 description 4
- 229910003472 fullerene Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- LQDBLQVSGVTZSP-UHFFFAOYSA-N 4,5-difluoro-2h-benzotriazole Chemical compound FC1=CC=C2NN=NC2=C1F LQDBLQVSGVTZSP-UHFFFAOYSA-N 0.000 description 2
- RJWOBTDUYSFUCP-UHFFFAOYSA-N 5-bromo-4-(2-ethylhexoxy)thiophene-3-carbaldehyde Chemical compound BrC1=C(C(=CS1)C=O)OCC(CCCC)CC RJWOBTDUYSFUCP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 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 2
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- ZKLBPUYMTHPNOQ-UHFFFAOYSA-N 5-bromothiophene-3-carbaldehyde Chemical compound BrC1=CC(C=O)=CS1 ZKLBPUYMTHPNOQ-UHFFFAOYSA-N 0.000 description 1
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 1
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
- BDEOXDSSZJCZPE-UHFFFAOYSA-N [1,3]thiazolo[4,5-d][1,3]thiazole Chemical compound N1=CSC2=C1N=CS2 BDEOXDSSZJCZPE-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000013087 polymer photovoltaic Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- YCQHVKQGWLAQMR-UHFFFAOYSA-N thieno[3,4-f][2]benzothiole-4,8-dione Chemical compound O=C1C2=CSC=C2C(=O)C2=CSC=C12 YCQHVKQGWLAQMR-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000584 ultraviolet--visible--near infrared spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
-
- 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
- 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
-
- 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
- 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
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/204—Applications use in electrical or conductive gadgets use in 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses an indacene A-D-A type conjugated micromolecule compound containing a hepta-fused ring structure, a preparation method thereof and application of the compound as an optical active layer material in an organic photovoltaic device. The compounds have the following general structure:
the photovoltaic cell is based on a hepta-fused ring as an electron supply unit (D), a thiophene ring as a bridging unit, and a thiophene 4-position as an electron pulling unit (A), and the energy level structure and the light absorption characteristic of the material are adjusted by utilizing the difference of the substitution positions of the A unit on the bridging thiophene, so that the parameters of the photovoltaic cell, such as open-circuit voltage, short-circuit current and the like, are adjusted, and the photoelectric conversion efficiency of the device is improved.
Description
Technical Field
The invention belongs to the field of organic photoelectric functional materials, and particularly relates to a derivative A-D-A type conjugated micromolecule compound containing a hepta-condensed ring structure, a preparation method thereof, and application of the molecule as an n-type material in an optical active layer in an Organic Photovoltaic (OPV) device.
Background
Among solar cells, organic solar cells have become one of the most active fields in photovoltaic research due to their advantages of light weight, low cost, simple preparation process, capability of being prepared into flexible devices, and the like. The photoactive layer material is a key photoactive layer of an organic solar cell, and its properties determine the generation and diffusion of excitons, the separation and transport of charges, and ultimately the photoelectric conversion efficiency of the cell.
The photoactive layer comprises an electron donor material and an electron acceptor material to form a bulk heterojunction, and a conjugated polymer as an electron donor and a fullerene derivative (PC)61BM、PC71BM, ICBA, etc.) as electron acceptors have made the efficiency of organic solar cells breakthrough 11% [ Nature Energy,2016,1,15027]Meaning a great potential for the application of organic solar cells. However, fullerenes and their derivatives have certain disadvantages including: harsh preparation and purification conditions, weak absorption in a visible light region, difficult energy level regulation, poor solubility in common solvents, easy aggregation and the like [ nat. photonics 2012,6,153]These disadvantages limit the further breakthrough of organic solar cell performance. In recent years, non-fullerene micromolecule electron acceptor materials attract attention of scientific researchers because of the advantages of simple preparation, strong absorption in the long wave direction, adjustable structure and energy level, excellent solubility and the like. Novel n-type electron acceptor materials based on imide, fluorenyl derivatives, benzothiazole, pyrrolopyrroledione, pentacene and the like are mainly used for photovoltaic cells. Perylene Diimides (PDI) are the first class of materials studied in solar cells, have excellent light absorption properties, broad solar spectrum, high electron mobility, tunable Highest Occupied Molecular Orbital (HOMO) and lowest unoccupied orbital (LUMO) energy levels, electron affinity comparable to fullerenes, and structurally, the imide can be modified by simple modificationAmine parent nucleus and side substituent, so as to obtain a series of n-type electron acceptor materials with excellent photoelectric property [ adv. Mater.2010,22,3876 ]]However, the wider band gap of such materials limits further improvement of device performance; pentacene and derivatives thereof are easy to regulate and control the film form through chemical modification so as to improve the charge transmission rate [ adv](ii) a Photovoltaic devices made from benzothiadiazole-based materials exhibit good electron transport properties [ adv]. Pyrrolopyrroledione (DPP) [ j]Has wide light absorption range, excellent electrochemical performance, thermodynamic stability and machining performance, and can meet the technological requirement of making organic electronic device. Zhan xiao wei et al [ j.mater.chem.a.2015,3,1910]The dithiophene indacene receptor-based molecules are developed, a pi conjugated framework is extended by fused rings, high electron mobility is obtained, in addition, due to the electron push-pull structure of the molecules, more efficient intramolecular charge transfer can be induced, so that the absorption spectrum of the material is widened, the absorption spectrum is blended with a narrow-band donor polymer material PTB7-Th, and the device efficiency reaches 6.31%. The micromolecule acceptor material generally has a penta-fused ring or hepta-fused ring structure, attracts wide attention due to excellent performance, and is used as an electron acceptor for preparing an organic photovoltaic cell, wherein the performance of the micromolecule acceptor material reaches or even exceeds that of a fullerene electron acceptor [ adv.mater.2016,28,1884; adv.mater.2016,28,4734; adv. mater.2016,28,9423]. In addition, in the reported structures, thiophene or bithiophene can be used as a bridging unit between the central condensed ring and the electricity-deficient units on two sides, and the photoelectric properties are excellent [ CN 105315298A; adv.mater.2016,28,8283; angew.chem.int.ed.2017,56,1]. The electricity-lacking units of the materials are limited to be connected to the 5-position of the thiophene bridging unit, the molecular frameworks of the materials are mostly in a planar structure, although the structure promotes the absorption spectrum of some of the materials to be red-shifted to a near infrared band, a single polymer donor material with good absorption spectrum matching property is difficult to find to form spectrum complementation with the material, and the photoelectric conversion efficiency of a binary-blended single-layer organic photovoltaic cell based on the small molecular receptors is generally less than 10%.
Disclosure of Invention
Aiming at the defects or shortcomings in the prior art, the invention provides a hepta-fused ring indacene A-D-A type micromolecule compound, wherein electricity-deficient units on two sides of the micromolecule are connected to 4-position of a thiophene bridging unit, the structure is not reported, and the structure can realize adjustment of photoelectric property so as to meet the requirement of a photovoltaic cell photoactivation layer electron acceptor material. The small molecular compound is used for a high-efficiency organic photovoltaic cell, and the energy level and the spectral range of the material are adjusted by utilizing the steric effect, the push-pull electronic characteristic of a substituent group and the like, so that the photoelectric conversion efficiency of the device is improved.
In order to realize the task, the structure of the A-D-A type micromolecule compound of the hepta-fused ring indacene designed by the invention is as follows:
wherein R is1Independently an alkyl group having 1 to 20 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 20 carbon atoms, a thienyl group substituted with an alkyl group having 1 to 20 carbon atoms, or a thienyl group substituted with an alkoxy group having 1 to 20 carbon atoms, R2Independently hydrogen atom, alkyl group with 1-20 carbon atoms, alkoxy group with 1-20 carbon atoms or alkyl ester group with 1-20 carbon atoms, wherein the electron withdrawing unit A1And A2Independently selected from one of the following structures:
A1and A2In the structure of R3Is an alkyl group having 1 to 12 carbon atoms.
The preparation method is carried out by adopting the following reaction equation:
the specific synthesis steps are as follows:
will carry R1Substituted hepta-fused ring organotin reagents, with R2Adding 5-bromo-3-thiophenecarboxaldehyde as a substituent into a reaction vessel, adding 5-10% of catalyst tetrakis (triphenylphosphine) palladium or bis (triphenylphosphine) palladium dichloride under the protection of argon, taking toluene as a solvent, carrying out micro reflux for 12-24h, stopping heating after the reaction is completed, cooling the system to room temperature, adding water to terminate the reaction, extracting an aqueous phase with toluene, carrying out liquid separation, drying and filtering on an organic layer, carrying out spin drying on the filtrate to obtain a crude product, purifying the crude product by column chromatography to obtain a corresponding hepta-condensed ring containing dialdehyde, and then mixing the aldehyde with a 4-6 times of electron withdrawing unit A1Or A2Adding pyridine into chloroform solution, refluxing for 6-12 hr, cooling, precipitating with methanol, performing silica gel column chromatography, and eluting with chloroform to obtain target product, or mixing the hepta-condensed ring containing dialdehyde with 1-1.5 times of A1Adding pyridine into chloroform solution for refluxing for 6-10 hr, purifying by column chromatography, mixing with 2-4 times of A2And adding pyridine into a chloroform solution by a unit pulling electron monomer, refluxing for 6-12 hours, extracting by chloroform, settling by methanol, carrying out silica gel column chromatography, and eluting by chloroform to obtain the A-D-A conjugated molecular product shown in the formula I.
Preferred embodiment of the invention, R1A 4-alkylphenyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a 5-alkylthienyl group having 1 to 20 carbon atoms, or a 4-alkoxyphenyl group having 1 to 20 carbon atoms; r2Is an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an alkyl ester group having 1 to 20 carbon atoms.
The indacene A-D-A type micromolecule compound containing the hepta-condensed ring structure provided by the invention can be used as an optical active layer material and applied to the preparation of organic photovoltaic cells.
The invention has the beneficial effects that: the invention introduces an electron-deficient unit to the 4-position of the thiophene ring, introduces a certain distortion on the molecular main chain, and effectively adjusts the absorption spectrum and the energy level of the material. The indacene A-D-A micromolecule compound has an absorption spectrum with adjustable width, a strong extinction coefficient, good charge transmission performance and a proper energy level structure, is mixed with a polymer electron donor with an optical band gap of 1.7-1.9 eV to manufacture a single-layer binary photovoltaic device, and the photoelectric conversion efficiency exceeds 10%. These wide-bandgap polymer electron donors include D-A type donor polymers based on difluorobenzotriazole, D-A type donor polymers based on thiazolothiazole, D-A type donor polymers based on benzo [1,2-C:4,5-C' ] dithiophene-4, 8-dione, and the like.
Drawings
FIG. 1 is a UV-VIS-NIR absorption spectrum of compound A1 of example 1 according to the invention.
FIG. 2 is a plot of the I-V curves of Compound A1 and a bis-fluorobenzotriazole polymer J52 of example 1 of the present invention.
Detailed Description
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1: compound A1
The synthetic route is as follows:
(1) synthesis of Compound 3:
a100 ml three-necked flask is added with 1672.5 mg/0.5mmol of compound, 478mg/1.5mmol of 2-bromo-3- (2-ethylhexyloxy) thiophene-4-formaldehyde and Pd (PPh)3)440mg of toluene 30ml, heating under nitrogen protection, refluxing for 24h, extracting, washing and performing column chromatography (n-hexane: ethyl acetate: 100:1) to obtain 550mg of compound 3 (liquid phase content)>99%) and 73.5% yield.1H NMR(500MHz,CDCl3),δ9.93(s,2H),7.94(s,2H),7.45(s,2H),7.18(d,8H),7.10(d,8H),6.88(s,2H),4.10(d,4H),2.57(t,8H),1.76(m,2H),1.66-1.58(m,16H),1.50-1.26(m,32H),0.95-0.86(m,24H).13C NMR(125MHz,CDCl3),δ181.09,164.32,157.11,153.37,146.23,142.93,141.91,139.04,137.06,135.16,129.62,128.45,127.68,126.39,122.71,119.30,117.72,111.12,74.46,63.07,39.43,35.52,31.65,31.28,30.32,29.07,29.01,23.78,22.94,22.55,14.04,14.02,11.10.Anal.Calcd for(C94H110O4S6):C 75.45,H 7.41,Found:C 75.23,H 7.27。
(2) Synthesis of A1
Placing 658mg/0.44mmol of the above compound 3, 575mg/2.5mmol of compound a in a 100ml three-necked flask, dissolving in 40ml of chloroform, adding pyridine 1.5ml, heating under reflux for 10h, stopping heating, cooling, extracting, washing, precipitating with methanol, filtering, purifying the obtained solid by column chromatography, eluting with chloroform to obtain 531mg of blue-black solid with yield of 65% and liquid phase content of liquid phase>99％。1H NMR(500MHz,CDCl3),δ9.17(s,2H)，8.66(d,2H),7.85(d,2H),7.73(m,4H),7.21(d,8H),7.14(d,8H),6.93(s,2H),4.18(q,4H),2.63(t,8H),1.91(m,2H),1.63-1.55(m,16H),1.36-1.29(m,32H),0.96-0.86(m,24H).13C NMR(125MHz,CDCl3),δ187.35,170.37,158.72,158.82,155.69,154.78,154.14,148.06,146.00,142.22,140.69,139.37,135.76,134.25,132.83,127.80,123.88,122.69,118.31,117.40,117.19,115.14,114.57,109.18,75.85,67.36,63.21,39.31,35.59,31.77,31.38,30.01,29.13,28.97,23.48,23.02,22.63,14.11,10.92.Anal.Calcd for(C118H114F4N4O4S6):C 73.79,H 5.98,Found:C 76.35,H 5.79。
The ultraviolet-visible-near infrared absorption spectra of the compound A1 solution and the film are shown in figure 1. The molar extinction coefficient of the solution of Compound A1, determined according to Lambert beer's law, was 3.94X 105M-1cm-1The optical energy gap obtained by the film absorption edge (843nm) test is 1.47 eV.
Photovoltaic performance study: adopts ITO/ZnO/J52 as receptor material/MoO3The polymer J52 and the acceptor material are made into polymer lightThe effective area of the photovoltaic cell is 0.16cm2In a simulated solar light source (Oriel model 91192; 100 mW/cm)2) Performing current-voltage test, collecting by using a Keithley 2400 source meter, and measuring the short-circuit current J of the devicescIs 21.17mA cm-2Open circuit voltage Voc0.84V, a fill factor of 66.4% and an energy conversion efficiency PCE of 11.83%. FIG. 2 shows the I-V curves of the polymer photovoltaic cells prepared from the compounds A1 and J52 according to a certain weight ratio in example 1.
The structural formula of J52 is shown below:
example 2: compound A2
The synthetic route is as follows:
placing 658mg/0.44mmol of the above compound 3, 485mg/2.5mmol of the compound b in a 100ml three-necked flask, dissolving in 40ml of chloroform, adding pyridine 1.5ml, heating and refluxing for 6h, stopping heating, cooling, extracting, washing, settling with methanol, filtering, purifying the obtained solid by column chromatography, eluting with chloroform to obtain 582mg of blue-black solid with yield of 69%, and collecting liquid phase content>99％。1H NMR(500MHz,CDCl3),δ9.17(s,2H)，8.66(d,2H),7.85(d,2H),7.72(m,4H),7.53(d,Hz,4H),7.19(d,8H),7.14(d,8H),6.93(s,2H),4.18(q,4H),2.63(t,8H),1.91(m,2H),1.62-1.55(m,16H),1.36-1.29(m,32H),0.96-0.86(m,24H).13C NMR(125MHz,CDCl3),δ187.25,170.27,158.71,158.82,154.78,154.14,145.99,142.22,140.69,139.37,137.06,135.76,134.25,132.83,128.69,127.79,123.88,122.69,118.31,117.40,117.19,115.14,114.57,109.18,75.85,67.36,63.20,39.31,35.58,31.77,31.38,30.01,29.13,28.97,23.48,23.02,22.63,14.11,10.92.Anal.Calcd for(C118H118N4O4S6):C 76.67,H 6.43,Found:C 76.15,H 6.28.
Example 3: synthesis of Compound A3
The synthetic route is as follows:
(1) synthesis of Compound 5:
in a 100ml three-necked flask, 1672.5 mg/0.5mmol of compound, 521mg/1.5mmol of 2-bromo-3-thiophenecarboxylic acid isooctyl ester-4-formaldehyde and Pd (PPh)3)440mg of toluene 30ml, heating under nitrogen protection, refluxing for 24h, extracting, washing and performing column chromatography (n-hexane: ethyl acetate: 100:1) to obtain 543mg of compound 5 (liquid phase content)>99%) and yield 70%.1H NMR(500MHz,CDCl3),δ9.93(s,2H),7.94(s,2H),7.46(s,2H),7.19(d,8H),7.11(d,8H),6.89(s,2H),4.30(d,4H),2.57(t,8H),1.81(m,2H),1.68-1.58(m,16H),1.50-1.26(m,32H),0.95-0.86(m,24H).13C NMR(125MHz,CDCl3),δ181.10,165.29,160.10,157.11,153.39,146.23,142.93,141.92,139.04,137.06,135.16,129.62,128.45,127.68,126.39,122.71,119.30,117.72,111.12,74.46,63.07,39.43,35.52,31.65,31.28,30.32,29.07,29.01,23.78,22.94,22.55,14.04,14.02,11.10.Anal.Calcd for(C96H110O6S6):C 74.28,H 7.14,Found:C 73.97,H 6.96.
(2) Synthesis of Compound A3
683mg/0.44mmol of the compound 5 and 485mg/2.5mmol of the compound b are put into a 100ml three-necked flask and dissolved in 40ml of chloroform, then 1.5ml of pyridine is added, heating reflux is carried out for 8h, heating is stopped, cooling, extraction and washing are carried out, methanol is used for sedimentation, the obtained solid is purified by column chromatography after filtration, chloroform is used for eluting and purifying562mg of bluish-black solid was obtained in 67% yield, liquid content>99％。1H NMR(500MHz,CDCl3),δ9.17(s,2H)，8.66(d,2H),7.85(d,2H),7.72(m,4H),7.53(d,Hz,4H),7.19(d,8H),7.14(d,8H),6.93(s,2H),4.31(q,4H),2.63(t,8H),2.01(m,2H),1.63-1.56(m,16H),1.38-1.30(m,32H),0.96-0.86(m,24H).13C NMR(125MHz,CDCl3),δ187.27,170.28,160.11,158.71,158.83,154.78,154.15,146.00,142.23,140.69,139.37,137.06,135.76,134.25,132.83,128.69,127.79,123.89,122.69,118.31,117.40,117.19,115.14,114.57,109.18,75.85,67.36,63.20,39.31,35.58,31.77,31.38,30.01,29.13,28.97,23.48,23.02,22.63,14.11,10.92.Anal.Calcd for(C120H118N4O6S6):C 75.67,H 6.24,Found:C 75.46,H 6.09.
Example 4: compound A4
The synthetic route is as follows:
(1) synthesis of compound 7:
a100 ml three-necked flask is added with 6520.5 mg/0.5mmol of compound, 478mg/1.5mmol of 2-bromo-3- (2-ethylhexyloxy) thiophene-4-formaldehyde and Pd (PPh)3)440mg of toluene 30ml, heating under nitrogen protection, refluxing for 24h, extracting, washing and performing column chromatography (n-hexane: ethyl acetate: 100:1) to obtain 423mg of compound 7 (liquid phase content)>99%) and yield 71%.1H NMR(500MHz,CDCl3),δ9.92(s,2H),7.91(s,2H),7.43(s,2H),6.87(s,2H),4.11(d,4H),2.57(t,8H),1.76(m,2H),1.66-1.58(m,16H),1.50-1.26(m,32H),0.95-0.86(m,24H).13C NMR(125MHz,CDCl3),δ181.09,164.32,157.11,153.37,146.23,142.93,139.04,129.62,128.45,126.39,121.76,119.30,117.72,111.12,74.46,63.07,39.43,35.52,31.65,31.28,30.32,29.07,29.01,23.78,22.94,22.55,14.04,14.02,11.10.Anal.Calcd for(C70H94O4S6):C 70.54,H 7.95,Found:C 70.32,H 7.68.
(2) Synthesis of A4
Putting 524mg/0.44mmol of the compound 7 and 575mg/2.5mmol of the compound a into a 100ml three-necked flask, dissolving in 40ml of chloroform, adding 1.5ml of pyridine, heating and refluxing for 10h, stopping heating, cooling, extracting, washing, settling with methanol, filtering, purifying the obtained solid by column chromatography, and eluting with chloroform to obtain 484mg of a bluish black solid with the yield of 68 percent and the liquid phase content of the product>99％。1H NMR(500MHz,CDCl3),δ9.17(s,2H)，8.66(d,2H),7.85(d,2H),7.73(m,4H),6.93(s,2H),4.18(q,4H),2.63(t,8H),1.91(m,2H),1.63-1.55(m,16H),1.36-1.29(m,32H),0.96-0.86(m,24H).13C NMR(125MHz,CDCl3),δ187.35,170.37,158.72,158.82,155.69,154.78,154.14,148.06,146.00,140.69,139.37,132.83,127.80,122.69,118.31,117.40,117.19,115.14,114.57,109.18,75.85,67.36,63.21,39.31,35.59,31.77,31.38,30.01,29.13,28.97,23.48,23.02,22.63,14.11,10.92.Anal.Calcd for(C94H98F4N4O4S6):C 69.86,H 6.11,Found:C 69.57,H5.92.
Example 5: compound A5
The synthetic route is as follows:
placing 658mg/0.44mmol of the above compound 3, 152mg/0.66mmol of compound a in a 100ml three-necked flask, dissolving in 40ml of chloroform, adding pyridine 1.5ml, heating and refluxing for 6h, stopping heating, stopping reaction, purifying the obtained product by column chromatography, adding 351mg/1.32mmol of compound c in a 100ml three-necked flask, adding chloroform 40ml, adding pyridine 1.5ml, heating and refluxing for 8h, stopping heating, cooling, extracting, washingWashing, precipitating with methanol, filtering, purifying the obtained solid by column chromatography, eluting with chloroform to obtain blue black solid 335mg, with yield of 39%, and liquid phase content>99％。1H NMR(500MHz,CDCl3),δ9.17(s,2H)，8.66(d,2H),7.85(d,2H),7.73(m,2H),7.21(d,8H),7.14(d,8H),6.93(s,2H),4.18(q,4H),2.63(t,8H),1.91(m,2H),1.63-1.55(m,16H),1.36-1.29(m,32H),0.96-0.86(m,24H).13C NMR(125 MHz,CDCl3),δ187.35,170.37,158.72,158.82,155.69,154.78,154.14,148.06,146.00,142.22,140.69,139.37,137.21,136.17,132.83,127.80,123.88,122.69,118.31,117.40,117.19,115.14,114.57,109.18,75.85,67.36,63.21,39.31,35.59,31.77,31.38,30.01,29.13,28.97,23.48,23.02,22.63,14.11,10.92.Anal.Calcd for(C118H112F6N4O4S6):C 72.44,H 5.77,Found:C 72.31,H 5.69.
Claims (8)
1. A kind of indacene A-D-A type micromolecule compound containing hepta-condensed ring structure is characterized in that the structural general formula is shown as formula I:
in the formula, R1Independently an alkyl group having 1 to 20 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms, or a phenyl group substituted with an alkoxy group having 1 to 20 carbon atoms; r2Independently hydrogen atom, alkyl group with 1-20 carbon atoms, alkoxy group with 1-20 carbon atoms or alkyl ester group with 1-20 carbon atoms, wherein the electron withdrawing unit A1And A2Independently selected from one of the following structures:
2. the indacene a-D-a type small molecule compound containing a hepta-fused ring structure according to claim 1, whereinIn that R is1Is a 4-alkylphenyl group having 1 to 20 carbon atoms, R2Is an alkoxy group having 1 to 20 carbon atoms.
3. The indacene a-D-a type small molecule compound containing a hepta-fused ring structure according to claim 1, wherein R is1Is an alkyl group having 1 to 20 carbon atoms, R2Is an alkoxy group having 1 to 20 carbon atoms.
4. The indacene a-D-a type small molecule compound containing a hepta-fused ring structure according to claim 1, wherein R is1Is a 4-alkoxyphenyl group having 1 to 20 carbon atoms, R2Is an alkoxy group having 1 to 20 carbon atoms.
5. The indacene a-D-a type small molecule compound containing a hepta-fused ring structure according to claim 1, wherein R is1Is a 4-alkylphenyl group having 1 to 20 carbon atoms, R2Is an alkyl group having 1 to 20 carbon atoms.
6. The indacene a-D-a type small molecule compound containing a hepta-fused ring structure according to claim 1, wherein R is1Is a 4-alkylphenyl group having 1 to 20 carbon atoms, R2Is an alkyl ester group having 1 to 20 carbon atoms.
7. The indacene A-D-A type small molecule compound containing hepta-condensed ring structure of any one of claims 1-6, which is used as a photoactive layer material alone or in a blend with other materials, and is applied to the preparation of an organic photovoltaic cell.
8. A method for preparing the indacene a-D-a type small molecule compound containing a hepta-fused ring structure according to claim 1, wherein the preparation steps are performed according to the reaction formula shown in formula II:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711077458.7A CN107778319B (en) | 2017-11-06 | 2017-11-06 | A-D-A type micromolecule compound containing hepta-fused ring structure indacene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711077458.7A CN107778319B (en) | 2017-11-06 | 2017-11-06 | A-D-A type micromolecule compound containing hepta-fused ring structure indacene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107778319A CN107778319A (en) | 2018-03-09 |
| CN107778319B true CN107778319B (en) | 2021-07-27 |
Family
ID=61432640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711077458.7A Active CN107778319B (en) | 2017-11-06 | 2017-11-06 | A-D-A type micromolecule compound containing hepta-fused ring structure indacene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107778319B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265468B (en) * | 2018-09-18 | 2021-06-08 | 四川大学 | Small molecule containing anti-aromatic indacenodithiophene unit and application thereof in organic photovoltaics |
| WO2020062254A1 (en) * | 2018-09-30 | 2020-04-02 | Southern University Of Science And Technology | Chlorine atoms induced molecular interlocked network in a non-fullerene acceptor |
| CN109776566B (en) * | 2019-01-23 | 2021-12-28 | 深圳大学 | A-D-A conjugated molecule based on multi-substituted benzocyclopentadienone derivative and application thereof |
| CN110606857A (en) * | 2019-09-25 | 2019-12-24 | 湘潭大学 | An A-D-A type organic small molecule based on nine-ring fusion aromatics and its preparation method and application |
| CN112209946A (en) * | 2020-09-15 | 2021-01-12 | 西安近代化学研究所 | Benzo-dithiophene-containing hepta-condensed ring main chain twisted small-molecule near-infrared absorption material, and preparation method and application thereof |
| CN112409375A (en) * | 2020-11-21 | 2021-02-26 | 东华理工大学 | Organic small-molecule photovoltaic material based on tetrazine derivative |
| CN115073488B (en) * | 2021-03-12 | 2023-11-28 | 中国科学院化学研究所 | Fully fused ring organic photovoltaic receptors and their preparation methods and applications |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150114418A (en) * | 2014-03-27 | 2015-10-12 | 주식회사 엘지화학 | Heterocyclic compound and organic solar cell comprising the same |
| CN105315298A (en) * | 2014-08-04 | 2016-02-10 | 中国科学院化学研究所 | A-D-A conjugated molecules based on hepta-condensed ring units and preparation method for A-D-A conjugated molecules and application of A-D-A conjugated molecules |
| CN106883247A (en) * | 2017-02-24 | 2017-06-23 | 武汉大学 | A D A conjugated molecules based on thieno cyclopentanedione derivative and preparation method thereof |
-
2017
- 2017-11-06 CN CN201711077458.7A patent/CN107778319B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150114418A (en) * | 2014-03-27 | 2015-10-12 | 주식회사 엘지화학 | Heterocyclic compound and organic solar cell comprising the same |
| CN105315298A (en) * | 2014-08-04 | 2016-02-10 | 中国科学院化学研究所 | A-D-A conjugated molecules based on hepta-condensed ring units and preparation method for A-D-A conjugated molecules and application of A-D-A conjugated molecules |
| CN106883247A (en) * | 2017-02-24 | 2017-06-23 | 武汉大学 | A D A conjugated molecules based on thieno cyclopentanedione derivative and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Energy-level modulation of non-fullerene acceptors to achieve high-efficiency polymer solar cells at a diminished energy offset;Zhongqiang Zhang;《Journal of Materials Chemistry A》;20170412(第20期);第80677-80681页 * |
| Investigating the crystalline nature, charge transport properties and photovoltaic performances of ladder-type donor based small molecules;Hua-Chun Wang;《RSC Advances》;20150915(第5期);第80677-80681页 * |
| Zhongqiang Zhang.Energy-level modulation of non-fullerene acceptors to achieve high-efficiency polymer solar cells at a diminished energy offset.《Journal of Materials Chemistry A》.2017,(第20期),第9649-9654页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107778319A (en) | 2018-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107778319B (en) | A-D-A type micromolecule compound containing hepta-fused ring structure indacene and preparation method thereof | |
| CN107814811B (en) | A-D-A type micromolecular compound of indacene and preparation method thereof | |
| CN106467547B (en) | Polycyclic-based non-fullerene solar cell receptor material and preparation method and application thereof | |
| CN106543201B (en) | A-D-A type conjugated molecule based on substituted indenothiophene fused ring unit and preparation method thereof | |
| CN114106353B (en) | Four polymerization complexes using phenanthroline imidazole derivative as ligand, preparation method and application thereof | |
| CN110922569B (en) | Donor-receptor type ultralow band gap conjugated polymer based on imide pyrazine heterocycle and preparation method and application thereof | |
| CN104672434B (en) | A kind of organic semiconducting materials and preparation method and application | |
| CN106831815B (en) | A kind of A-D-A type small organic molecule receptor of seven yuan of condensed ring of carbazoles containing thieno and preparation method thereof | |
| CN104031245B (en) | A kind of Polymer photovoltaic materials, preparation method and its usage | |
| CN105153189A (en) | Narrow-band-gap oligomer containing quinone type Methyl-Dioxocyano-Pyridine unit, and preparation method and application thereof | |
| CN110483555B (en) | A class of D(π-A)2-type small molecule donor materials based on pyrazindole terminal acceptors and their preparation methods and applications | |
| CN113563374A (en) | A class of organic small molecule donor photovoltaic materials and their preparation methods and applications | |
| Chen et al. | Solution-processable tetrazine and oligothiophene based linear A–D–A small molecules: Synthesis, hierarchical structure and photovoltaic properties | |
| CN112209946A (en) | Benzo-dithiophene-containing hepta-condensed ring main chain twisted small-molecule near-infrared absorption material, and preparation method and application thereof | |
| CN109517142B (en) | Star-shaped D-A structure conjugated molecule based on tri-indeno five-membered aromatic heterocycle, and preparation method and application thereof | |
| KR101707028B1 (en) | Novel organic semiconductor compounds containing benzothiadiazole group, its manufacturing method and organic semiconductor device using the same | |
| CN108084409B (en) | Wide-band-gap organic semiconductor material and preparation method and application thereof | |
| CN109956955B (en) | Star-shaped D-A structure conjugated molecules based on benzotris (cyclopentadienobis five-membered aromatic heterocycles) and their preparation methods and applications | |
| CN111039961A (en) | Preparation and application of oligomer photovoltaic donor material based on 5, 6-difluo benzothiadiazole unit | |
| CN106589325B (en) | A kind of conjugated polymer containing benzo[c]cinnoline and its synthesis method and application | |
| CN107778280B (en) | Small molecule acceptor material for star-shaped symmetrical organic solar cell based on trimeric indene, preparation method thereof, and organic solar cell | |
| US11114619B2 (en) | Conjugated polymer for a photoactive layer, a coating composition including the conjugated polymer, and an organic solar cell including the photoactive layer | |
| CN116375732B (en) | A non-fullerene acceptor material and its preparation method and application | |
| CN108659002A (en) | The conjugation small molecule electron-acceptor material and preparation method thereof in active layer is blended in polymer solar battery | |
| CN110669349A (en) | A class of phenothiazine dyes and their applications in dye-sensitized solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |