CN106977491B - Spiro [ fluorene-9, 9-xanthene ] hole transport material and application thereof - Google Patents
Spiro [ fluorene-9, 9-xanthene ] hole transport material and application thereof Download PDFInfo
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- CN106977491B CN106977491B CN201710060589.8A CN201710060589A CN106977491B CN 106977491 B CN106977491 B CN 106977491B CN 201710060589 A CN201710060589 A CN 201710060589A CN 106977491 B CN106977491 B CN 106977491B
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- Prior art keywords
- fluorene
- spiro
- xanthene
- transport material
- alkyl
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- 239000000463 material Substances 0.000 title claims abstract description 71
- QQNLHOMPVNTETJ-UHFFFAOYSA-N spiro[fluorene-9,9'-xanthene] Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC=CC=C2C2=CC=CC=C21 QQNLHOMPVNTETJ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000005525 hole transport Effects 0.000 title claims description 42
- -1 arylamine compound Chemical class 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 125000005647 linker group Chemical group 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims abstract description 15
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 35
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 125000002541 furyl group Chemical class 0.000 claims description 4
- 125000001544 thienyl group Chemical class 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 12
- 230000009477 glass transition Effects 0.000 abstract description 10
- 125000003003 spiro group Chemical group 0.000 abstract description 8
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 7
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 10
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 10
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 5
- CKZFMJJZECAJCW-UHFFFAOYSA-N spiro[fluorene-9,9'-xanthene]-2,7-diamine Chemical compound C1=CC=CC=2OC3=CC=CC=C3C3(C1=2)C1=CC(=CC=C1C=1C=CC(=CC=13)N)N CKZFMJJZECAJCW-UHFFFAOYSA-N 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- CYGGERDBQBUNDY-UHFFFAOYSA-N 2,7-dibromospiro[fluorene-9,9'-xanthene] Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC(Br)=CC=C2C2=CC=C(Br)C=C21 CYGGERDBQBUNDY-UHFFFAOYSA-N 0.000 description 4
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000004896 high resolution mass spectrometry Methods 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005580 one pot reaction Methods 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 4
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 description 3
- MNBDZJINQUZDFP-UHFFFAOYSA-N 2-bromospiro[fluorene-9,9'-xanthene] Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC=CC=C2C2=CC=C(Br)C=C21 MNBDZJINQUZDFP-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VCOONNWIINSFBA-UHFFFAOYSA-N 4-methoxy-n-(4-methoxyphenyl)aniline Chemical compound C1=CC(OC)=CC=C1NC1=CC=C(OC)C=C1 VCOONNWIINSFBA-UHFFFAOYSA-N 0.000 description 2
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- LOYYIKDGYOYCSH-UHFFFAOYSA-N [Co].N1(N=CC=C1)C1=NC=CC=C1.N1(N=CC=C1)C1=NC=CC=C1.N1(N=CC=C1)C1=NC=CC=C1 Chemical compound [Co].N1(N=CC=C1)C1=NC=CC=C1.N1(N=CC=C1)C1=NC=CC=C1.N1(N=CC=C1)C1=NC=CC=C1 LOYYIKDGYOYCSH-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 235000008434 ginseng Nutrition 0.000 description 2
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000012925 reference material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 125000005259 triarylamine group Chemical group 0.000 description 2
- UPJLZKCEPFAKSH-UHFFFAOYSA-N 2',7'-dibromo-9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC(Br)=CC=C1C1=CC=C(Br)C=C12 UPJLZKCEPFAKSH-UHFFFAOYSA-N 0.000 description 1
- QQTBEFPDRHYPLE-UHFFFAOYSA-N 2,7-dibromo-9,9-dipropylfluorene Chemical compound C1=C(Br)C=C2C(CCC)(CCC)C3=CC(Br)=CC=C3C2=C1 QQTBEFPDRHYPLE-UHFFFAOYSA-N 0.000 description 1
- JUZPYVOOFVEYJW-UHFFFAOYSA-N 2,7-dibromo-9-(4-methoxyphenyl)carbazole Chemical compound BrC1=CC=2N(C3=CC(=CC=C3C=2C=C1)Br)C1=CC=C(C=C1)OC JUZPYVOOFVEYJW-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001894 space-charge-limited current method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- 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
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract
Spiro [ fluorene-9, 9-xanthene]The hole-like transport material is spiro [ fluorene-9, 9-xanthene ] and its application]The arylamine compound is of a core-shell structure, the compound contains more than 1N-core structural unit, two adjacent N-core structural units are connected through a connecting group, and the N-core structural unit conforms to a general formula F: rx, Ry and Rz are substituents or linking groups. The material of the invention is polyspiro [ fluorene-9, 9-xanthene]Is arylamine compound with core-shell structure. Compared with the existing like products, the glass transition temperature and the thermal decomposition temperature are higher; has higher oxidation-reduction potential; higher hole mobility and conductivity; the method has great application value and wide application prospect in the field of perovskite solar cells and other organic electronic devices.
Description
Technical Field
The invention relates to a spiro [ fluorene-9, 9-xanthene ] hole transport material and a preparation method thereof, and relates to application of the material in the fields of perovskite solar cells, organic electroluminescent devices, organic field effect transistors, organic photodetectors, organic lasers, organic nonlinear optics, organic electrical storage, chemical and biological sensing and the like. Belongs to the technical field of organic semiconductors and photoelectric materials.
Technical Field
Since 2009, Tsutomu Miyasaka, professor Tsutomu university of tung shadow shores, japan, first reported a perovskite-based crystal structure (CH)3NH3PbX3X represents a halogen element) as a light absorbing material (j.am.chem.soc.,2009,131(17), pp 6050-. The efficiency of perovskite solar cells has improved from the first 3.8% to 22.1% in the past short 7 years (Nature Energy, 2016, doi: 10.1038/nergy.2016.142). The efficiency of the solar cell can be completely compared with the photoelectric conversion efficiency of a crystalline silicon solar cell. More importantly, the perovskite crystal material has a high molar extinction coefficient which is as high as 105. By adjusting the composition of the perovskite material, the band gap and the absorption spectrum of the perovskite material can be changed, and battery devices with various colors can be prepared. In addition, the perovskite solar cell has the advantages of low cost, simple preparation process, capability of preparing flexible, transparent and laminated cells and the like, thereby showing wide application prospect.
The hole transport material is generally used between a perovskite layer and a metal electrode to improve Schottky (Schottky) contact, promote separation of electrons and holes at a functional layer interface, reduce charge recombination, facilitate hole transport and improve battery performance. Currently, the most widely used organic small-molecule hole transport material 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group in perovskite solar cells]9,9' -spirobifluorene (spiro-OMeTAD) with the photoelectric conversion efficiency of 21.6 percent. However, the synthesis of the 9, 9-spirobifluorene with the core-shell structure of the molecule needs to use an anhydrous and oxygen-free reaction, and has the disadvantages of multiple steps, low total yield and limited large-scale preparation. More importantly, the hole migration of spiro-OMeTADThe mobility and the conductivity are low, the thermal stability is poor, the oxidation-reduction potential is low, and the use is limited to a certain extent. Monospiro [ fluorene-9, 9-xanthene]Nuclear hole transport materials, such as X59, although simpler to synthesize, are due to their glass transition temperature (T)g) And thermal decomposition temperature (T)d) The hole mobility and the conductivity are not high, and the application of the perovskite battery is limited.
In addition, the photoelectric conversion efficiency of the poly triarylamine hole transport material (PTAA) is as high as more than 20%, but the poly triarylamine hole transport material has more synthesis steps, is difficult to purify and has higher production cost, and the future large-scale application of the perovskite solar cell is greatly limited. Therefore, the development of low-cost, high-efficiency, high-stability and market-potential organic hole transport materials for perovskite solar cells has attracted extensive attention and investment by scientists and various large enterprises all over the world.
It can be seen from the above that, although the existing spiro [ fluorene-9, 9-xanthene ] hole transport materials have a vertical spiro structure and can effectively inhibit pi-pi stacking between molecules, thereby having excellent performances in various aspects such as solubility and thermal stability, various defects still exist and limit practical commercial applications.
Disclosure of Invention
One of the purposes of the invention is to optimally design and improve the structure of the compound with the structure based on the existing spiro [ fluorene-9, 9-xanthene ] hole transport material so as to obtain a material substance with more excellent market application value.
Based on the above, the invention firstly provides a spiro [ fluorene-9, 9-xanthene ] hole transport material, which is an arylamine compound with spiro [ fluorene-9, 9-xanthene ] as a core-shell structure, wherein the compound contains more than 1N-core structural unit, two adjacent N-core structural units are connected through a connecting group, and the N-core structural unit conforms to the general formula F:
rx, Ry and Rz are substituents or linking groups;
wherein the substituents are each independently R, phenyl or substituted phenyl;
the substituted phenyl is phenyl optionally substituted by the following groups: halogen, -OH, C1-6Alkyl or C1-6An alkoxy group;
the linking group is selected from groups of formulae i to xv:
in the substituent group represented by the formula R and the linking group represented by the formulae i to xv, R1～21Each independently selected from-H, halogen, -OH, C1-6Alkyl radical, C1-6Alkyl-substituted phenyl radical, C1-6Alkoxy-substituted phenyl radical, C1-6Alkyl-substituted thienyl or C1-6Alkyl substituted furyl.
The spiro [ fluorene-9, 9-xanthene ] hole transport materials of the present invention are actually arylamine compounds containing a polyspiro [ fluorene-9, 9-xanthene structure. Compared with the arylamine organic hole transport material with a core-shell structure of single spiro [ fluorene-9, 9-xanthene ] in the prior art, the compound has the following outstanding advantages:
① higher glass transition temperature (T)g) And thermal decomposition temperature (T)d) Showing better thermal stability;
②, a higher oxidation-reduction potential is beneficial to obtaining a higher open-circuit voltage in the perovskite solar cell device;
③, higher hole mobility and conductivity, facilitating more efficient charge separation and transport in perovskite solar cell devices;
④ has good solubility in chlorobenzene, o-dichlorobenzene and toluene, which is beneficial to the preparation of organic film by solution method;
⑤ the synthesis and purification method is simple, which is beneficial to large-scale commercial preparation;
⑥ has good device performance in perovskite solar cells, the photoelectric conversion efficiency of the device is as high as more than 20%, and the device has potential for commercial application.
The series of compounds as organic hole transport materials have great application value and wide application prospect in the field of perovskite solar cells and other organic electronic devices, and specific application fields can be exemplified but not limited to organic solar cells, organic electroluminescent devices, organic field effect transistors, organic photodetectors, organic lasers, organic nonlinear optics, organic electrical storage, chemical and biological sensing and the like.
Therefore, the invention also provides the application of the spiro [ fluorene-9, 9-xanthene ] hole transport material in the preparation of perovskite solar cells.
Drawings
The invention is illustrated in figure 3, wherein:
FIG. 1 is a structural schematic diagram of a standard device of a perovskite solar cell.
FIG. 2 is an electrochemical cyclic voltammogram of a reference material.
Fig. 3 is a voltage and current density plot of a perovskite solar cell device of the materials tested.
Detailed Description
The spiro [ fluorene-9, 9-xanthene ] hole transport material has a vertical spiro structure, so that the spiro [ fluorene-9, 9-xanthene ] hole transport material can effectively inhibit pi-pi accumulation among molecules, and has excellent solubility and thermal stability. The invention provides a novel spiro [ fluorene-9, 9-xanthene ] hole transport material, which is an arylamine compound with a spiro [ fluorene-9, 9-xanthene ] core-shell structure, wherein the compound contains more than 1N-core structural unit, two adjacent N-core structural units are connected through a connecting group, and the N-core structural units conform to the general formula F:
the spiro [ fluorene-9, 9-xanthene ] hole transport material provided by the invention is essentially an arylamine compound with a multispiro [ fluorene-9, 9-xanthene ] core-shell structure, and has a basic structural unit shown as a general formula F, namely an N-core structural unit which repeatedly appears in the compound. Two adjacent N-core structural units are connected through a connecting group, so that the extension of the molecular formula is realized.
In the spiro [ fluorene-9, 9-xanthene ] hole transport material, at least one of Rx, Ry and Rz in the general formula F is a connecting group, so as to ensure that 2 or more than 2N-nuclear structural units in the compound are connected. In general, two adjacent N-core building blocks of the present invention share the same linking group. This repeating N-nuclear structural unit, which appears in the present invention, aims to provide a plurality of spiro [ fluorene-9, 9-xanthenes ] and a plurality of N-nuclear arylamine centers. The number of occurrence of the N-nuclear structural unit of the formula F, namely the number of the N-nuclear structural units contained in the compound is 2-10, preferably 2-6. The number of N-nuclear structural units in the compound and the choice of Rx, Ry and Rz together determine the number of spiro [ fluorene-9, 9-xanthene ] structural units in the compound. Or more specifically, the number of spiro [ fluorene-9, 9-xanthene ] structural units can be expressed as the total number of groups of structure R or formula x in the compound. For the purpose of the present invention, it is required that the number of spiro [ fluorene-9, 9-xanthene ] structural units is 2 or more. Preferably, the total number of spiro [ fluorene-9, 9-xanthene ] structural units in the compound is 3-7.
As described above, in the general formula F of the present invention, 1 or 2 of Rx, Ry and Rz are a substituent; the substituents are each independently R, phenyl or substituted phenyl;
in the substituent of the formula R, in the connecting group, R1And R2Each independently selected from-H, halogen, -OH, C1-6Alkyl radical, C1-6Alkyl-substituted phenyl radical, C1-6Alkoxy-substituted phenyl radical, C1-6Alkyl-substituted thienyl or C1-6An alkyl-substituted furyl group; preferably, R is1And R2Each independently selected from-H, halogen, -OH, C1-6Alkyl radical, C1-6Alkyl-substituted phenyl radical, C1-6Alkoxy substituted phenyl. In a more preferred embodiment, R is1And R2Each independently selected from-H, C1-6Alkyl radical, C1-6Alkyl-substituted phenyl and C1-6Alkoxy substituted phenyl. In the above structure, spiro [ fluorene-9, 9-xanthene ] is involved]Structural, and even more preferably xanthene structural units are preferably symmetrically treated, including but not limited to both H substitutions, i.e., unsubstituted structures.
Most preferably, R is1And R2Are all H.
The substituted phenyl group mentioned hereinabove is a phenyl group optionally substituted with: halogen, -OH, C1-6Alkyl or C1-6An alkoxy group; any substitution referred to in this specification, unless otherwise indicated, shall be construed in accordance with the ordinary understanding of the art, and such optionally substituted phenyl groups shall mean any number of substituents substituted at any position on the phenyl group.
Preferably, the substituents are each independently R, phenyl, C1-6Alkyl-optionally substituted phenyl, C1-6Alkoxy-optionally substituted phenyl; more preferably, the substituents are each independently R, phenyl, C1-6Alkoxy monosubstituted phenyl; further preferred are R, phenyl and C1-6Alkoxy para-substituted phenyl; most preferred are R, phenyl and C1-4Alkoxy para-substituted phenyl; r, phenyl and p-methoxyphenyl are particularly preferred, wherein R1And R2Is H.
In formula F of the present invention, at least 1 linking group selected from the group consisting of Rx, Ry and Rz is selected from the group consisting of groups of formulae i to xv:
in the above-mentioned linking group, R3～21Each independently selected from-H, halogen, -OH, C1-6Alkyl radical, C1-6Alkyl-substituted phenyl radical, C1-6Alkoxy-substituted phenyl radical, C1-6Alkyl-substituted thienyl or C1-6An alkyl-substituted furyl group; preferably, R is3～21Each independently selected from-H, halogen, -OH, C1-6Alkyl radical, C1-6Alkyl-substituted phenyl radical, C1-6Alkoxy substituted phenyl. In a more preferred embodiment, R is3～21Each independently selected from-H, C1-6Alkyl radical, C1-6Alkyl-substituted phenyl and C1-6Alkoxy substituted phenyl.
In a more specific embodiment, the linking group referred to in the present invention is selected from the following groups:
wherein linking groups of the formulae i, ii or x are furthermore preferred.
In the above description of the structure relating to the linking group, it is particularly preferred that the xanthene building blocks, which relate to the spiro [ fluorene-9, 9-xanthene ] structure, are preferably treated symmetrically, including but not limited to all H substitutions, i.e. unsubstituted structures.
More specifically, the spiro [ fluorene-9, 9-xanthene ] hole transport material of the present invention is a compound selected from the following structures:
especially preferred are compounds of formulae X26, X36, X37, X54, X55 and X56, respectively:
x26: n2- (2- (bis (4-methoxybenzene) amine) spiro [ fluorene-9, 9 '-xanthen ] -7-yl) -N2, N7, N7-tetrakis (4-methoxybenzene) spiro [ fluorene-9, 9' -xanthene ] -2, 7-diamine;
x36: n2, N2 "- ([1,1' -biphenyl ] -4,4' -diyl) bis (N2, N7, N7-tetrakis (4-methoxybenzene) spiro [ fluorene-9, 9' -xanthene ] -2, 7-diamine;
x37: n2, N2 "- (spiro [ fluorene-9, 9 '-xanthene ] -2, 7-diyl) bis (N2, N7, N7-tetrakis (4-methoxybenzene) spiro [ fluorene-9, 9' -xanthene ] -2, 7-diamine;
x54: n4, N4' -bis (4-methoxybenzene) spiro-N4, N4' -dispiro [ fluorene-9, 9' -xanthen ] -2-yl) - [1,1' -biphenyl ] -4,4' -diamine;
x55: n2, N7-bis (4-methoxybenzene) -N2, N7-dispiro [ fluorene-9, 9 '-xanthen ] -2-yl) spiro [ fluorene-9, 9' -xanthen ] -2, 7-diamine;
x56: n2, N2, N7, N7-tetrakis (spiro [ fluorene-9, 9 '-xanthen ] -2-yl) spiro [ fluorene-9, 9' -xanthene ] -2, 7-diamine.
The preparation method of the spiro [ fluorene-9, 9-xanthene ] hole transport material adopts different synthesis schemes according to the number of different N-nuclear structure units required to be prepared. Depending on the number of N-nuclear structural units and the number of spiro [ fluorene-9, 9-xanthenes ] in the target product, a person skilled in the art can specify suitable synthesis schemes according to the prior art. The applicant first provided a more specific class of synthesis methods, aiming at guiding the skilled person to use similar methods to accomplish the synthesis of other compounds. The synthesis method comprises the following steps:
(1) dried toluene, 3 molar parts of 2, 7-dibromospiro [ fluorene-9, 9-xanthene ], 0.02 molar part of palladium acetate, 0.04 molar part of 1,1 '-bis (diphenylphosphino) ferrocene, 1 molar part of 4,4' -dimethoxydiphenylamine and 1.5 molar parts of sodium tert-butoxide (0.29g,3.0mmol) were added to a two-necked flask at room temperature under nitrogen protection and stirred overnight at 100 ℃. After cooling, the reaction was quenched with water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and chromatographed on silica gel to give a pale yellow solid which was identified as 7-bromo-N, N-bis (4-methoxybenzene) spiro [ fluorene-9, 9' -xanthene ] -2-amine, TBrSFX.
(2)2.2 molar parts of TBrSFX,1 molar part of p-anisidine, 2.5 molar parts of sodium tert-butoxide, 0.01 molar part of palladium acetate, 0.01 molar part of tri-tert-butylphosphine and dry toluene are added into a Schlenk bottle, the reaction system is replaced by a double-row pipe for three times to remove water and oxygen, then the temperature is raised to 100 ℃, and the reaction is carried out overnight. After cooling, the reaction was quenched with water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and separated by silica gel column chromatography to give a pale yellow solid powder, X26.
(3) The final product was prepared using a one-pot Buchwald (Buchwald) reaction: dried toluene, 0.06 parts by mole of tris (dibenzylideneacetone) dipalladium, 0.1 parts by mole of 1,1' -bis (diphenylphosphino) ferrocene (DPPF) and 1 part by mole of 2, 7-dibromospiro [ fluorene-9, 9-xanthene ], (or 4,4' -dibromo-1, 1' -biphenyl, or 2, 7-dibromo-9- (4-methoxyphenyl) -9H-carbazole, or 2, 7-dibromo-9, 9-dipropyl-9H-fluorene, or 2, 7-dibromo-9, 9' -spirobifluorene, or 2, 7-dibromospiro [ fluorene-9, 9' -thianthrene ]10',10' -dioxo) were added to a two-necked flask and stirred at room temperature for 10 minutes under nitrogen protection. Subsequently, 2.5 parts by mole of sodium t-butoxide and 2 parts by mole of p-anisidine were added to this solution, and the temperature was raised to 90 ℃ to react for 8 hours. After this time, follow-up by TLC spot plate until the starting material spot disappears. Then, 2.5 parts by mole of sodium tert-butoxide, 2.1 parts by mole of 2-bromospiro [ fluorene-9, 9-xanthene ] (or 7-bromo-N, N-bis (4-methoxybenzene) spiro [ fluorene-9, 9' -xanthene ] -2-amine (TBrSFX)) and toluene were added. The solution was warmed to 100 ℃ and stirred overnight. After the reaction, the reaction mixture was cooled, quenched with water, extracted with ethyl acetate, dried with sodium sulfate, and separated by silica gel column chromatography to obtain pale yellow solid powders X36, X37, X54, X55, X56, X57, X58, X67, X68, and X55, respectively.
The above processes describe the preparation of X26, X36, X37, X54, X55, X56, X57, X58, X67, X68 and X55. By simple transformation of the process, the corresponding starting materials are selected, for example, the corresponding R is used in step (1)2And R3Substituted dibromospiro [ fluorene-9, 9-xanthenes]As raw materials, the corresponding position in the obtained product has R2And R3Substituted products. While R can be realized completely independently by the person skilled in the art according to the prior art2And R3Substituted dibromospiro [ fluorene-9, 9-xanthenes]And the present invention has been completed.
On the other hand, the highly preferred compounds X26, X36, X37, X54, X55, X56, X57, X58, X67, X68 and X55 described in detail in the above process contain 2 to 4N-core structural units. The compound containing 4-10N-nuclear structural units can be obtained by repeatedly using a simple chemical reaction method, such as Buchwald (Buchwald) and Suzuki (Suzuki), and selecting corresponding raw material reactants. The applicant believes that the skilled person in the art can completely design and implement a corresponding method to complete the synthesis according to the structure of the target product and by combining the description of the synthesis method, thereby achieving the aim of the invention.
The following non-limiting examples are intended to further illustrate the present invention and should not be construed as limiting the invention in any way.
Example 1
Synthesis of N2- (2- (bis (4-methoxybenzene) amine) spiro [ fluorene-9, 9 '-xanthen ] -7-yl) -N2, N7, N7-tetrakis (4-methoxybenzene) spiro [ fluorene-9, 9' -xanthen ] -2, 7-diamine (X26) according to the following route:
(1) synthesis of 7-bromo-N, N-bis (4-methoxybenzene) spiro [ fluorene-9, 9' -xanthene ] -2-amine (TBrSFX):
dried toluene (20ml), 2, 7-dibromospiro [ fluorene-9, 9-xanthene ] (2.94g,6.0mmol), palladium acetate (9.0mg,0.04mmol),1,1 '-bis (diphenylphosphino) ferrocene (44.4mg,0.08mmol),4,4' -dimethoxydiphenylamine (0.46g,2.0mmol) and sodium tert-butoxide (0.29g,3.0mmol) were added to a two-necked flask at room temperature under nitrogen protection and stirred at 100 deg.C overnight. After cooling, the reaction was quenched with water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and separated by silica gel column chromatography to give 1.00g of a pale yellow solid with a yield of 78%. Identified as 7-bromo-N, N-bis (4-methoxybenzene) spiro [ fluorene-9, 9' -xanthen ] -2-amine.
1H NMR(400MHz,d6-DMSO,298K),δ(ppm):7.78(d,J＝8Hz,1H),7.75(d,J＝8Hz,1H),7.51(d,J＝8Hz,1H),7.27～7.24(m,4H),7.08(s,1H),6.91(d,J＝8Hz,6H),6.80(d,J＝4Hz,5H),6.49(s,1H),6.42(d,J＝8Hz,2H),3.68(s,6H,OMe)。
(2) Synthesis of N2- (2- (bis (4-methoxybenzene) amine) spiro [ fluorene-9, 9 '-xanthen ] -7-yl) -N2, N7, N7-tetrakis (4-methoxybenzene) spiro [ fluorene-9, 9' -xanthen ] -2, 7-diamine (X26):
TBrSFX (639mg,1.00mmol), p-anisidine (56mg,0.46mmol), sodium tert-butoxide (109mg,1.14mmol), palladium acetate (4mg,0.02mmol), tri-tert-butylphosphine (4mg,0.02mmol) and 10mL toluene were added to a 50mL Schlenk flask, the reaction was replaced three times with double calandria to remove water and oxygen, then warmed to 100 ℃ and reacted overnight. After cooling, the reaction was quenched with water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and separated by silica gel column chromatography to give a pale yellow solid, 461mg, yield 81%. Was identified as N2- (2- (bis (4-methoxybenzene) amine) spiro [ fluorene-9, 9 '-xanthen ] -7-yl) -N2, N7, N7-tetrakis (4-methoxybenzene) spiro [ fluorene-9, 9' -xanthene ] -2, 7-diamine (X26).
1H NMR(400MHz,d6-DMSO,298K),δ(ppm):7.58(d,J＝8Hz,2H),7.53(d,J＝8Hz,2H),7.22(t,J＝8Hz,4H),7.11(d,J＝8Hz,4H),6.91～6.67(m,26H),6.62(d,J＝8Hz,2H),6.53(s,2H),6.48(s,2H),6.42(d,J＝8Hz,4H),3.68(s,12H,OMe),3.63(s,3H,OMe).13CNMR(400MHz,C6D6,298K),δ(ppm):156.91,156.50,156.28,156.14,151.88,149.01,147.83,141.37,140.61,134.75,132.68,126.95,126.53,125.92,123.56,121.27,120.75,120.01,118.56,117.15,114.94,114.78,54.98,54.88,54.68.HR-MS(ESI)m/z:[M+1]+calcd for 1237.4666；found,1238.4619.
Example 2
Synthesis of N2, N2 "- ([1,1' -biphenyl ] -4,4' -diyl) bis (N2, N7, N7-tetrakis (4-methoxybenzene) spiro [ fluorene-9, 9' -xanthene ] -2, 7-diamine (X36) according to the following route:
specifically, a one-pot Buchwald (Buchwald) reaction is utilized to prepare a final product: dried toluene (10mL), tris (dibenzylideneacetone) dipalladium (3.1mg,0.03mmol), 1,1' -bis (diphenylphosphino) ferrocene (DPPF) (5.2mg,0.05mmol) and 4,4' -dibromo-1, 1' -biphenyl (156mg,0.5mmol) were added to a two-necked flask under nitrogen at room temperature and stirred for 10 minutes. Subsequently, sodium tert-butoxide (120mg,1.25mmol) and p-anisidine (123mg,1.00mmol) were added to the solution, and the temperature was raised to 90 ℃ to react for 8 hours. After this time, follow-up by TLC spot plate until the starting material spot disappears. Then, sodium tert-butoxide (120mg,1.25mmol), TBrSFX (670.5mg,1.05mmol) and toluene were added. The solution was warmed to 100 ℃ and stirred overnight. After completion of the reaction, the reaction was cooled, quenched with water, extracted with ethyl acetate, dried over sodium sulfate, and separated by silica gel column chromatography to give 590mg of a pale yellow solid in 78% yield. Was identified as N2, N2 "- ([1,1' -biphenyl ] -4,4' -diyl) bis (N2, N7, N7-tetrakis (4-methoxybenzene) spiro [ fluorene-9, 9' -xanthene ] -2, 7-diamine
1H NMR(400MHz,d6-DMSO,298K),δ(ppm):7.66(d,J＝8Hz,2H),7.62(d,J＝8Hz,2H),7.31～7.23(m,8H),7.13(d,J＝8Hz,4H),6.93～6.71(m,36H),6.65(s,2H),6.50(d,J＝8Hz,6H),3.68(s,6H,OMe),3.70(s,12H,OMe).13C NMR(400MHz,C6D6,298K),δ(ppm):156.75,156.68,156.47,156.34,151.95,149.13,147.98,147.27,141.36,140.85,134.73,134.58,132.95,127.51,127.44,126.60,126.00,123.58,123.37,123.26,121.31,120.80,120.28,120.16,118.60,117.26,115.07,114.97,55.05,54.89.HR-MS(ESI)m/z:[M+1]+calcd for 1510.5820；found,1511.5848.
Example 3
Synthesis of N4, N4' -bis (4-methoxybenzene) spiro-N4, N4' -dispiro [ fluorene-9, 9' -xanthen ] -2-yl) - [1,1' -biphenyl ] -4,4' -diamine (X54) according to the following scheme:
the final product was prepared using a one-pot Buchwald (Buchwald) reaction: dried toluene (10mL), tris (dibenzylideneacetone) dipalladium (6.2mg,0.06mmol), 1,1' -bis (diphenylphosphino) ferrocene (DPPF) (10.3mg,0.1mmol) and 4,4' -dibromo-1, 1' -biphenyl (312mg,1.00mmol) were added to a two-necked flask under nitrogen at room temperature and stirred for 10 minutes. Subsequently, sodium tert-butoxide (240mg,2.50mmol) and p-anisidine (246mg,2.00mmol) were added to the solution, and the temperature was raised to 90 ℃ to react for 8 hours. After this time, follow-up by TLC spot plate until the starting material spot disappears. Then, sodium tert-butoxide (120mg,1.25mmol), 2-bromospiro [ fluorene-9, 9-xanthene ] (863.7mg,2.10mmol) and toluene were added. The solution was warmed to 100 ℃ and stirred overnight. After completion of the reaction, the reaction was cooled, quenched with water, extracted with ethyl acetate, dried over sodium sulfate, and separated by silica gel column chromatography to give 856mg of a pale yellow solid in 81% yield. Identified as N4, N4' -bis (4-methoxybenzene) spiro-N4, N4' -dispiro [ fluorene-9, 9' -xanthen ] -2-yl) - [1,1' -biphenyl ] -4,4' -diamine (X54).
1H NMR(400MHz,d6-DMSO,298K),δ(ppm):7.85(t,J＝8Hz,4H),7.35(d,J＝8Hz,6H),7.28～7.21(m,8H),7.14(t,J＝8Hz,2H),7.03～6.83(m,20H),6.68(s,2H),6.42(d,J＝8Hz,4H),3.71(s,6H,OMe).13C NMR(400MHz,C6D6,298K),δ(ppm):156.99,156.91,155.61,151.95,149.10,147.16,140.68,139.91,134.96,134.27,127.58,126.08,125.65,123.67,123.54,122.95,121.02,120.36,119.48,117.19,115.12,54.93,54.89.HR-MS(ESI)m/z:[M+1]+calcd for 1056.3927；found,1056.3943.
Example four
Synthesis of N2, N7-bis (4-methoxybenzene) -N2, N7-dispiro [ fluorene-9, 9 '-xanthen ] -2-yl) spiro [ fluorene-9, 9' -xanthen ] -2, 7-diamine (X55) according to the following synthetic route:
the final product was prepared using a one-pot Buchwald (Buchwald) reaction: dried toluene (10mL), tris (dibenzylideneacetone) dipalladium (6.2mg,0.06mmol), 1,1' -bis (diphenylphosphino) ferrocene (DPPF) (10.3mg,0.1mmol) and 2, 7-dibromospiro [ fluorene-9, 9-xanthene ] (4.90mg,1.0mmol) were added to a two-necked flask under nitrogen at room temperature and stirred for 10 minutes. Subsequently, sodium tert-butoxide (240mg,2.50mmol) and p-anisidine (246mg,2.00mmol) were added to the solution, and the temperature was raised to 90 ℃ to react for 8 hours. After this time, follow-up by TLC spot plate until the starting material spot disappears. Then, sodium tert-butoxide (120mg,1.25mmol), 2-bromospiro [ fluorene-9, 9-xanthene ] (863.7mg,2.10mmol) and toluene were added. The solution was warmed to 100 ℃ and stirred overnight. After completion of the reaction, the reaction mixture was cooled, quenched with water, extracted with ethyl acetate, dried over sodium sulfate, and separated by silica gel column chromatography to obtain 1037mg of a pale yellow solid with a yield of 84%. Identified as N2, N7-bis (4-methoxybenzene) -N2, N7-dispiro [ fluorene-9, 9 '-xanthen ] -2-yl) spiro [ fluorene-9, 9' -xanthene ] -2, 7-diamine (X55).
1H NMR(400MHz,d6-DMSO,298K),δ(ppm):7.80(d,J＝8Hz,2H),7.73(d,J＝8Hz,2H),7.59(d,J＝8Hz,2H),7.33～7.19(m,12H),7.11(t,J＝8Hz,4H),6.97(d,J＝8Hz,2H),6.88～6.85(m,10H),6.77(d,J＝8Hz,4H),6.65(d,J＝8Hz,4H),6.56(d,J＝8Hz,4H),6.39(d,J＝8Hz,2H),6.34(d,J＝8Hz,4H),3.63(s,6H,OMe).13C NMR(400MHz,C6D6,298K),δ(ppm):156.69,155.82,151.87,151.77,148.85,147.86,140.35,139.61,134.45,134.29,128.18,127.95,127.15,125.94,125.57,123.66,123.59,122.94,122.53,120.84,120.78,120.34,120.23,119.44,117.16,117.11,114.81,54.90,54.85,54.68.HR-MS(ESI)m/z:[M+1]+calcd for1234.4346；found,1234.4359.
Example 5
Test of Oxidation-reduction potential of hole transport Material
The materials tested were X59, X26, X36, X55 and Spiro-OMeTAD, respectively. Wherein X59 and Spiro-OMeTAD are mononuclear materials, X26 and X36 are binuclear materials, and X55 is a trinuclear material.
Electrochemical Cyclic Voltammetry (CV) was tested on an electrochemical workstation (model 660A) using a three electrode, Ag/0.01M AgNO3As reference electrode, glassy carbon as working electrode, platinum wire as counter electrode, dichloromethane as solvent, hexafluorophosphoric tetrabutyl amine (n-Bu)4NPF6) As electrolyte, a concentration of 0.1M was used, a sweep rate of 50mV/s, based on ferrocene. The CV diagram is shown in the attached FIG. 2, and the data obtained by converting the oxidation-reduction potential into a standard hydrogen electrode is shown in Table 1.
From fig. 2, we can convert the oxidation-reduction potential values of the reference materials into: x59 was 0.61V, X26 was 0.66V, X36 was 0.68V, X55 was 0.73V, and spiro-OMeTAD was 0.62V (see Table 1). Therefore, the oxidation-reduction potential of the polynuclear spiro [ fluorene-9, 9-xanthene ] hole transport material is generally higher than that of a mononuclear hole transport material.
TABLE 1
Example 6
Test for hole mobility and conductivity of hole transport material
The materials tested were the same as in example 5.
The hole mobility and the conductivity of such hole transport materials were respectively tested by a space charge limited current method and a two-point probe method. The device structure of hole mobility is: ITO/PEDOT PSS/spiro [ fluorene-9, 9-xanthene ] hole transport material layer/molybdenum trioxide/metal electrode. The device structure of conductivity is: glass substrate/porous titanium dioxide layer/spiro [ fluorene-9, 9-xanthene ] type hole transport material layer/metal electrode. The hole transport material layer is prepared by a spin coating method, and is doped with 4-tert-butylpyridine (TBP), lithium bis (trifluoromethanesulfonyl) imide (lithium bis (trifluoromethylsulfonyl) imide, Li-TFSI) and p-type dopant tris (2- (1Hpyrazol-1-yl) pyridine) cobalt (III), FK102) in dry chlorobenzene at a concentration of 70 mg/mL.
The hole mobility and conductivity data calculated by fitting are shown in table 1. From the data in the table, we can see that the hole mobility and the electric conductivity of the polynuclear spiro [ fluorene-9, 9-xanthene ] type hole transport materials (X26, X36 and X55) are generally higher than those of the single nucleus (X59 and spiro-OMeTAD).
Example 7
Different hole transport materials are used for manufacturing the perovskite solar cell device, and the photoelectric conversion efficiency of the perovskite solar cell device is detected. Materials tested included Spiro-OMeTAD (mononuclear), X26 (binuclear), X36 (binuclear), and X55 (trinuclear).
The device structure is as follows: FTO/dense titanium dioxide layer/porous titanium dioxide layer/perovskite light absorption layer/spiro [ fluorene-9, 9-xanthene ] hole transport material layer/metal electrode. The hole transport material layer is prepared by a spin coating method, and is doped with 4-tert-butylpyridine (TBP), lithium bis (trifluoromethanesulfonyl) imide (lithium bis (trifluoromethylsulfonyl) imide, Li-TFSI) and p-type dopant tris (2- (1Hpyrazol-1-yl) pyridine) cobalt (III), FK102) in dry chlorobenzene at a concentration of 70 mg/mL. The photoelectric conversion efficiency of the device is shown in an attached figure 3, and specific parameters are shown in a table 2.
TABLE 2
| Ginseng testing material | Photoelectric conversion efficiency | Open circuit voltage | Short circuit current | Fill factor |
| Spiro-OMeTAD | 18.8 | 1.13 | 23.1 | 72.0 |
| X26 | 20.2 | 1.11 | 24.3 | 74.5 |
| X36 | 18.9 | 1.06 | 23.7 | 76.0 |
| X55 | 20.8 | 1.15 | 23.4 | 77.4 |
From the results in Table 2, it can be seen that the hole transport materials (X26, X36 and X55) of the polynuclear spiro [ fluorene-9, 9-xanthene ] type have higher photoelectric conversion efficiency and higher short-circuit current density than the single-nucleus spiro-OMeTAD.
Example 8
Glass transition temperature (Tg) and decomposition temperature test (Td) for hole transport materials
The materials tested were X26, X36, X55, X39, X56, X57, X58 and Spiro-OMeTAD, respectively. Wherein Spiro-OMeTAD is a mononuclear material, X26 and X36, X39 and X58 are binuclear materials, X55 and X57 are trinuclear materials, and X56 is a pentanuclear material.
In the experiment, Differential Scanning Calorimetry (DSC) is adopted to test the glass transition temperature (Tg) of the series of materials, the model of the used instrument is Mettler Toledo, the sweeping speed is 10 ℃/min under the nitrogen atmosphere, and the glass transition temperature of the materials can be obtained through the obtained differential scanning calorimetry curve. The thermogravimetric analysis (TGA) tester is Mettler Toledo, the sweeping speed is 10 ℃/min under the nitrogen atmosphere, and the glass transition temperature of the material can be obtained through the initial point of the obtained thermogravimetric analysis curve. The specific glass transition temperature and thermal decomposition temperature of the material are shown in table 3.
As can be seen from the data measured in Table 3, the glass transition temperature and thermal decomposition temperature of the hole transport material of the polynuclear spiro [ fluorene-9, 9-xanthene ] type are generally higher than those of the mononuclear nucleus.
TABLE 3
| Ginseng testing material | X26 | X36 | X39 | X55 | X56 | X57 | X58 | Spiro |
| Glass transition temperature | 155.2 | 164.6 | 181.5 | 175.4 | 192.8 | 179.3 | 160.1 | 121.1 |
| Temperature of thermal decomposition | 438.2 | 439.0 | 441.5 | 446.4 | 457.8 | 446.1 | 437.6 | 421.9 |
Claims (7)
1. The spiro [ fluorene-9, 9-xanthene ] cavity transport material is an arylamine compound with spiro [ fluorene-9, 9-xanthene ] as a core-shell structure, and is characterized in that the compound contains 2-4N-core structure units, two adjacent N-core structure units are connected through a connecting group, and the N-core structure units conform to a general formula F:
rx, Ry and Rz are a substituent or a linking group, at least one of which is a linking group;
wherein the substituents are each independently R, phenyl or substituted phenyl;
the substituted phenyl is phenyl optionally substituted by the following groups: halogen, -OH, C1-6Alkyl or C1-6An alkoxy group;
the linking group is selected from groups of formulae i to xv:
in the substituent group represented by the formula R and the linking group represented by the formulae i to xv, R1～21Each independently selected from-H, halogen, -OH, C1-6Alkyl radical, C1-6Alkyl-substituted phenyl radical, C1-6Alkoxy-substituted phenyl radical, C1-6Alkyl-substituted thienyl or C1-6An alkyl-substituted furyl group;
the total number of groups with the structure of R or the formula x in the compound is 2-5.
2. Spiro [ fluorene-9, 9-xanthene ] according to claim 1]The hole-like transport material is characterized in that in the substituent group of the formula R and the connecting group of the formulas i to xv, R is1～21Each independently selected from-H, halogen, -OH, C1-6Alkyl radical, C1-6Alkyl-substituted phenyl radical, C1-6Alkoxy substituted phenyl.
3. Spiro [ fluorene-9, 9-xanthene ] according to claim 2]A hole-like transport material, wherein R is1～21Each independently selected from-H, C1-6Alkyl radical, C1-6Alkyl-substituted phenyl and C1-6Alkoxy substituted phenyl.
4. A spiro [ fluorene-9, 9-xanthene ] based hole transport material according to claim 3, wherein the linking group is selected from the group consisting of:
5. spiro [ fluorene-9, 9-xanthene ] according to claim 3]The hole-like transport material is characterized in that the substituents are respectively and independently R, phenyl and C1-6Alkyl-optionally substituted phenyl, C1-6Alkoxy optionally substituted phenyl.
6. A spiro [ fluorene-9, 9-xanthene ] based hole transport material according to claim 1, characterized by being selected from compounds of the following structures:
7. use of the spiro [ fluorene-9, 9-xanthene ] based hole transport material according to claim 1 in the preparation of perovskite solar cells.
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| CN112250677A (en) * | 2020-10-16 | 2021-01-22 | 南昌航空大学 | Organic small molecule hole transport material based on spiro [ fluorene-9, 9' -xanthene ], preparation method and application thereof |
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