CN105694853B - 一种有机发光材料及其制备方法和应用 - Google Patents
一种有机发光材料及其制备方法和应用 Download PDFInfo
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- 239000011368 organic material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 230000008859 change Effects 0.000 claims abstract description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 3
- 239000011343 solid material Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 14
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- TWEILHAJXWAJIW-UHFFFAOYSA-N benzo[e][1,2,3]benzothiadiazole Chemical class C1=CC2=CC=CC=C2C2=C1SN=N2 TWEILHAJXWAJIW-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000012074 organic phase Substances 0.000 description 13
- MKYQPGPNVYRMHI-UHFFFAOYSA-N Triphenylethylene Chemical group C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 MKYQPGPNVYRMHI-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- UDGKZGLPXCRRAM-UHFFFAOYSA-N 1,2,5-thiadiazole Chemical class C=1C=NSN=1 UDGKZGLPXCRRAM-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 8
- MPFYNGAGLNSXOL-UHFFFAOYSA-N benzo[f][2,1,3]benzothiadiazole Chemical class C1=C2C=CC=CC2=CC2=NSN=C21 MPFYNGAGLNSXOL-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000013517 stratification Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000003756 stirring 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 4
- 230000005526 G1 to G0 transition Effects 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- -1 xenyl Chemical group 0.000 description 2
- ABEVIHIQUUXDMS-UHFFFAOYSA-N (2-bromophenyl)-phenylmethanone Chemical compound BrC1=CC=CC=C1C(=O)C1=CC=CC=C1 ABEVIHIQUUXDMS-UHFFFAOYSA-N 0.000 description 1
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- OVUYEFLHMIBQIP-UHFFFAOYSA-N benzo[g][2,1,3]benzothiadiazole Chemical class C1=CC2=CC=CC=C2C2=NSN=C21 OVUYEFLHMIBQIP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- XTBLDMQMUSHDEN-UHFFFAOYSA-N naphthalene-2,3-diamine Chemical class C1=CC=C2C=C(N)C(N)=CC2=C1 XTBLDMQMUSHDEN-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/84—Naphthothiazoles
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- C09K9/02—Organic tenebrescent materials
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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Abstract
本发明提供了一种有机发光材料,其结构式如通式I所示,其中,Ar选自芳香基或芳杂环基团,R1、R2、R3分别选自H、C1~C12烷基。本发明还提供了上述发光材料的制备方法,本发明以萘并噻二唑为核心单元,在分子内引入四苯基乙烯衍生物单元和芳香基(或杂环基团)。本发明在压力作用下可以产生固体颜色和荧光的变化,这种压致变色性质在光电领域具有非常重要的作用。
Description
技术领域
本发明属于材料学领域,涉及一种有机发光材料,具体来说是一种含萘并[2,3-c][1,2,5]噻二唑和四苯乙烯结构的发光材料及其制备方法和应用。
背景技术
压致变色是指当施加外力刺激,如研磨、剪切、拉伸、压力等,材料颜色,特别是荧光(如发光强度、发射波长)等发生明显变化的一种现象,经过溶剂熏蒸或热处理,其可以可逆的变回初始状态。压致变色材料是一类新型的刺激响应型智能材料引起了人们极大的关注,其在信息存储、商品防伪、微应力传感、安全油墨和发光器件等领域具有重要的应用前景。相对于传统的无机及配合物压致变色材料,有机压致变色材料具有许多突出的优点,如结构性能易修饰性、易于加工成膜等。但是,目前还少见报道有机压致变色发光材料。此外,通常的固态下的有机发光材料由于高浓度下的聚集猝灭效应(M.D.Curtis,et al.,J.Am.Chem.Soc.,2004,126,4318-4328;Y.Hong,et al.,Chem.Soc.Rev.,2011,40,5361-5388),导致发光效率降低或者不发光,极大的限制了有机压致变色发光材料的发展。因此,开发具有高固态发光效率、结构和制备工艺简单的低成本有机压致变色发光材料对发展刺激响应型智能材料及其应用具有重大的现实意义。
发明内容
针对现有技术中的上述技术问题,本发明提供了一种有机发光材料及其制备方法和应用,所述的这种有机发光材料及其制备方法和应用要解决现有技术中的有机压致变色材料发光效率低、合成路线复杂、成本较高的技术问题。
本发明提供了一种有机发光材料,其结构式如通式I所示,
其中,Ar选自芳香基或芳杂环基团,R1、R2、R3分别选自H、C1~C12烷基。
进一步的,所述的Ar为苯基、萘基、蒽基、联苯基、呋喃基或噻吩基,R1、R2、R3分别选自H。
进一步的,所述的Ar为苯基,R1、R2、R3均为H。
本发明还提供了上述的有机发光材料的制备方法,包括如下步骤:
1)一个制备4-芳香基(或芳杂环基)-9-溴萘并[2,3-c][1,2,5]噻二唑的步骤,在所述的制备4-芳香基(或芳杂环基)-9-溴萘并[2,3-c][1,2,5]噻二唑的步骤中,在氮气保护下,将4,9-二溴萘并[2,3-c][1,2,5]噻二唑,芳香基(或芳杂环基)硼酸,碳酸钾水溶液,四氢呋喃或甲苯或乙醇,四三苯基膦钯加入反应体系中,于40℃至回流温度下,反应6-24小时,得到4-芳香基(或芳杂环基)-9-溴萘并[2,3-c][1,2,5]噻二唑,其结构式如下所示,
2)一个制备烷基取代的4-芳香基(或芳杂环基)-9-[4-(1,2,2-三苯乙烯基)苯基]萘并[2,3-c][1,2,5]噻二唑的步骤,在所述的制备烷基取代的4-芳香基(或芳杂环基)-9-[4-(1,2,2-三苯乙烯基)苯基]萘并[2,3-c][1,2,5]噻二唑的步骤中,氮气保护下,将4-芳香基(或芳杂环基)-9-溴萘并[2,3-c][1,2,5]噻二唑、烷基取代的4-(1,2,2-三苯乙烯基)苯硼酸,碳酸钾水溶液,四氢呋喃或甲苯或乙醇,四三苯基膦钯加入反应体系中,于40℃至回流温度下,反应6-24小时,得到烷基取代的4-芳香基(或芳杂环基)-9-[4-(1,2,2-三苯乙烯基)苯基]萘并[2,3-c][1,2,5]噻二唑,结构式如下所示,
进一步的,在所述的制备4-芳香基(或芳杂环基)-9-溴萘并[2,3-c][1,2,5]噻二唑的步骤中,在一个反应容器中,加入4,9-二溴萘并[2,3-c][1,2,5]噻二唑,氮气保护下,依次加入芳香基(或芳杂环基)硼酸,碳酸钾水溶液,四氢呋喃或甲苯或乙醇,所述的4,9-二溴萘并[2,3-c][1,2,5]噻二唑、芳香基(或芳杂环基)硼酸、碳酸钾水溶液、四氢呋喃或甲苯或乙醇、四三苯基膦钯的摩尔体积比为2.0~3.0mmol:2.0~3.0mmol:5~15mL:10~30mL:0.05~0.3mmol,碳酸钾水溶液的浓度为1.0~4.0mol/L,于40℃至回流温度下,反应6-24小时,冷却后,静置分层,分出有机相,水相用有机溶剂萃取,合并有机相,饱和食盐水洗涤,有机相用无水硫酸钠干燥、抽滤、滤饼用有机溶剂洗涤后,将滤液与洗涤液合并,真空浓缩后,柱层析分离,得4-芳香基(或芳杂环基)-9-溴萘并[2,3-c][1,2,5]噻二唑,其结构式如下所示。
进一步的,在所述的制备烷基取代的4-芳香基(或芳杂环基)-9-[4-(1,2,2-三苯乙烯基)苯基]萘并[2,3-c][1,2,5]噻二唑的步骤中,在另外一个反应容器中,加入4-芳香基(或芳杂环基)-9-溴萘并[2,3-c][1,2,5]噻二唑,氮气保护下,依次加入烷基取代的4-(1,2,2-三苯乙烯基)苯硼酸,碳酸钾水溶液,四氢呋喃或甲苯或乙醇,四三苯基膦钯,所述的4-芳香基(或芳杂环基)-9-溴萘并[2,3-c][1,2,5]噻二唑、烷基取代的4-(1,2,2-三苯乙烯基)苯硼酸、碳酸钾水溶液、四氢呋喃或甲苯或乙醇、四三苯基膦钯的摩尔体积比为2.0~3.0mmol:2.0~3.0mmol:5~15mL:10~30mL:0.05~0.3mmol,碳酸钾水溶液的浓度为1.0~4.0mol/L,于40℃至回流温度下,反应6-24小时,冷却后,静置分层,分出有机相,水相用有机溶剂萃取,合并有机相,饱和食盐水洗涤,有机相用无水硫酸钠干燥、抽滤、滤饼用有机溶剂洗涤后,将滤液与洗涤液合并,真空浓缩后,柱层析分离,得到烷基取代的4-芳香基(或芳杂环基)-9-[4-(1,2,2-三苯乙烯基)苯基]萘并[2,3-c][1,2,5]噻二唑,结构式如下所示,
本发明还提供了上述有机发光材料在压致变色性能中的应用。
具体的,在压力作用下,固体材料的颜色和/或荧光发生改变。
本发明还提供了上述有机发光材料在制备记忆芯片、商标防伪、微应力传感、安全油墨或者发光器件中的应用。
本发明还提供了一种有机发光材料,其结构式如通式II所示,
其中,R1、R2、R3分别选自H、C1~C12烷基。
进一步的,R1、R2、R3分别选自H。
本发明还提供了上述的有机发光材料的制备方法,在氮气保护下,将4,9-二溴萘并[2,3-c][1,2,5]噻二唑,烷基取代的4-(1,2,2-三苯乙烯基)苯硼酸,碳酸钾水溶液,四氢呋喃或甲苯或乙醇,四三苯基膦钯加入反应体系中,于40℃至回流温度下,反应6-24小时,得到烷基取代的4,9-二[4-(1,2,2-三苯乙烯基)苯基]萘并[2,3-c][1,2,5]噻二唑,结构式如下所示,
进一步的,在所述的制备烷基取代的4,9-二[4-(1,2,2-三苯乙烯基)苯基]萘并[2,3-c][1,2,5]噻二唑的步骤中,在一个反应容器中,加入4,9-二溴萘并[2,3-c][1,2,5]噻二唑,氮气保护下,依次加入烷基取代的4-(1,2,2-三苯乙烯基)苯硼酸,碳酸钾水溶液,四氢呋喃或甲苯或乙醇,四三苯基膦钯,所述的4,9-二溴萘并[2,3-c][1,2,5]噻二唑、烷基取代的4-(1,2,2-三苯乙烯基)苯硼酸、碳酸钾水溶液、四氢呋喃或甲苯或乙醇、四三苯基膦钯的摩尔体积比为2.0~3.0mmol:4.0~6.6mmol:5~30mL:10~60mL:0.1~0.6mmol,碳酸钾水溶液的浓度为1.0~4.0mol/L,于40℃至回流温度下,反应6-24小时,冷却后,静置分层,分出有机相,水相用有机溶剂萃取,合并有机相,饱和食盐水洗涤,有机相用无水硫酸钠干燥、抽滤、滤饼用有机溶剂洗涤后,将滤液与洗涤液合并,真空浓缩后,柱层析分离,得到烷基取代的4,9-二[4-(1,2,2-三苯乙烯基)苯基]萘并[2,3-c][1,2,5]噻二唑,结构式如下所示,
即得到相应的具有压致变色性能的有机发光材料。
本发明还提供了上述的有机发光材料在压致变色性能中的应用。
具体的,在压力作用下,固体材料的颜色和/或荧光发生改变。
本发明还提供了上述的有机发光材料在制备记忆芯片、商标防伪、微应力传感、安全油墨或者发光器件中的应用。
上述含萘并[2,3-c][1,2,5]噻二唑和四苯乙烯结构的有机发光材料的合成路线如下所示:
本发明以萘并噻二唑为核心单元,在分子内引入四苯基乙烯衍生物单元和芳香基(或杂环基团),其合成方法简单,合成步骤较少、而且原料成本低廉,工艺易于工业化生产,产品提纯高效便捷,所制备的发光材料具有高的发光效率和强度,在压力作用下可以产生固体颜色和荧光的变化。并可通过连接不同基团调节化合物的发光性能。
本发明和已有技术相比,其技术进步是显著的。本发明所述的具有压致变色性能的有机发光材料具有高的发光效率和发光强度,可作为智能材料应用于光电领域。本发明对于制备记忆芯片、商标防伪、微应力传感、安全油墨和发光器件等方面均具有重要意义。
附图说明
图1是实施例2中,本发明提供的有机发光材料TPE-NTZ-B压力作用前后的荧光发射光谱图,横坐标为波长,纵坐标为归一化后的荧光强度;
图2是实施例3中,本发明提供的有机发光材料TPE-NTZ-TPE-1压力作用前后的荧光发射光谱图,横坐标为波长,纵坐标为归一化后的荧光强度。
具体实施方式
下面通过实施例对本发明作进一步的阐述,其目的仅在于更好地理解本发明的内容。因此,所举之例并不限制本发明的保护范围。
下列实施例中所说的室温是:25-28℃;所用原料及试剂均为市售品。
实施例1(有机发光材料的合成):
(1)化合物I-1的合成
具体制备步骤如文献(M.Banerjee,et al.,J.Org.Chem.,2007,72,8054-8061)所述。
二苯基甲烷(3.53g,21.0mmol)溶解于20mL无水四氢呋喃中,冷却至0℃,滴加1.6M正丁基锂/正己烷溶液(12.5mL,20.0mmol),搅拌30min后,体系成橙红色,再冷却至-78℃,将4-溴-二苯甲酮(5.22g,20.0mmol)与15mL无水四氢呋喃组成的溶液滴加到体系中,-78℃搅拌3h后,升温至室温,搅拌16h。加入20mL饱和氯化铵水溶液猝灭反应,静置分层,水相用二氯甲烷(30mL×3)进行萃取,合并有机相用饱和食盐水(20mL×2)洗涤,加入无水硫酸镁干燥。过滤后,滤液浓缩至干。在残留液中加入80mL甲苯和对甲苯磺酸(0.5g,2.6mmol)。采用分水器分水,加热回流6h。冷却至室温,用10%的碳酸氢钠水溶液(30mL×2)洗涤,加入无水硫酸钠干燥。用二氯甲烷和乙醇的混合溶液(v:v=1:6)进行重结晶,得4.10g白色固体I-1,产率80%。1HNMR(400MHz,CDCl3)δ(ppm):6.88(d,2H),6.99-7.03(m,6H),7.09-7.14(m,9H),7.21(d,2H).13C NMR(100MHz,CDCl3)δ(ppm):120.4,126.6,126.6,126.7,127.7,127.8,127.9,130.8,131.2,131.2,131.3,133.0,139.6,141.6,142.7,143.2,143.3,144.4.
(2)化合物II的合成
将化合物I-1(4.10g,10.0mmol)溶解于30mL无水四氢呋喃中,冷却至-78℃,滴加1.6M正丁基锂/正己烷溶液(7.5mL,12.0mmol),搅拌2h,将硼酸三异丙酯(2.45g,13.0mmol)快速滴加到体系中,于-78℃搅拌1h后,升温至室温,搅拌12h。加入稀盐酸溶液(2mol/L,10mL)猝灭反应,静置分层,水相用二氯甲烷(30mL×3)萃取,合并有机相用饱和食盐水(20mL×2)洗涤,加入无水硫酸钠干燥。过滤后,滤液浓缩至干。在粗品中加入石油醚(25mL)回流30min,得到3.20g白色固体II-1,产率85%。
1HNMR(400MHz,DMSO-d6)δ(ppm):6.90-6.96(m,8H),7.07-7.13(m,9H),7.50(d,2H),7.94(s,2H).13C NMR(100MHz,DMSO-d6)δ(ppm):126.4,127.6,129.5,130.4,133.4,140.5,143.0,144.7.
(3)化合物III的合成
具体制备步骤如文献(P.Wei,et al.,J.Mater.Chem.,2008,18,806-818)所述。
在室温下,将溴水(11.1g,69.5mmol)滴加到2,3-二氨基萘(5.0g,31.6mmol)和200mL冰醋酸组成的溶液中,搅拌2h。加入600mL冰水,析出大量固体。过滤,滤饼用水洗涤。得到褐色固体粉末7.80g,产率78%。在0℃下,将该褐色固体(7.80g,24.7mmol)与200mL形成的溶液缓慢滴加到由氯化亚砜(20.6g,173mmol)、70mL氯仿和30mL吡啶组成的溶液中。滴加结束后,在室温下搅拌2h,然后升温至回流,持续搅拌2h。溶液浓缩后,以硅胶为固定相,石油醚为洗脱剂柱层析分离,得3.12g固体III,产率37%。
1H NMR(400MHz,CDCl3)δ(ppm):7.65(dd,2H,J 7.0Hz,3.2Hz),8.46(dd,2H,J7.0Hz,3.2Hz).13C NMR(100MHz,CDCl3)δ(ppm):112.6,127.9,128.7,128.8,129.5,133.2,150.5.
(4)化合物IV-1的合成
氮气保护下,依次将化合物III(1.0g,2.90mmol)、苯硼酸(0.354g,2.90mmol)、2mol/L碳酸钾水溶液(30mL),重蒸四氢呋喃(60mL)、四三苯基膦钯(0.167g,0.145mmol)加入反应瓶中,加热回流12h。自然冷却后,静置分层,水相用二氯甲烷(30mL×3)进行萃取,合并有机相用饱和食盐水(20mL×2)洗涤,加入无水硫酸钠干燥。过滤后,滤液浓缩至干。以硅胶为固定相,石油醚:二氯甲烷=5:1为洗脱剂柱层析分离,得0.627g橙黄色固体IV-1,产率64%。
(5)有机发光材料PTE-NTZ-B的合成
氮气保护下,依次将化合物IV-1(0.751g,2.2mmol)、化合物II-1(0.998g,2.64mmol)、2mol/L碳酸钾水溶液(20mL),重蒸四氢呋喃(40mL)、四三苯基膦钯(0.254g,0.220mmol)加入反应瓶中,加热回流16h。自然冷却后,静置分层,水相用二氯甲烷(40mL×3)进行萃取,合并有机相用饱和食盐水(20mL×2)洗涤,加入无水硫酸钠干燥。过滤后,滤液浓缩至干。以硅胶为固定相,石油醚:二氯甲烷=7:3为洗脱剂柱层析分离,得0.982g红色固体TPE-NTZ-B,产率77%。
1H NMR(400MHz,CDCl3)δ(ppm):7.12-7.26(m,15H),7.31(d,2H,J 8.4Hz),7.36-7.39(m,2H),7.44(d,4H,J 8.4Hz),7.56-7.62(m,1H),7.63-7.68(m,4H),7.91-7.94(m,1H),7.98-8.02(m,1H).13C NMR(100MHz,CDCl3)δ(ppm):126.2,126.3,126.6,126.6,126.7,127.0,127.1,127.4,127.7,127.8,128.3,128.5,128.6,130.7,131.2,131.3,131.4,131.5,132.0,134.5,136.6,140.8,141.7,143.4,143.6,143.6,143.8.HR-EIMS m/z:[M]+calcd.for C42H28N2S,592.1973;found,592.1972.
(6)有机发光材料PTE-NTZ-PTE-1的合成
氮气保护下,依次将化合物III(0.618g,1.50mmol)、化合物II-1(1.24g,3.30mmol)、2mol/L碳酸钾水溶液(15mL),重蒸四氢呋喃(30mL)、四三苯基膦钯(0.173g,0.150mmol)加入反应瓶中,加热回流20h。自然冷却后,静置分层,水相用二氯甲烷(40mL×3)进行萃取,合并有机相用饱和食盐水(20mL×2)洗涤,加入无水硫酸钠干燥。过滤后,滤液浓缩至干。以硅胶为固定相,石油醚:二氯甲烷=6:4为洗脱剂柱层析分离,得0.982g橙色固体TPE-NTZ-TPE-1,产率77%。
1H NMR(400MHz,THF-d6)δ(ppm):6.97-7.09(m,30H),7.13(d,4H,J 8.0Hz),7.23(dd,2H,J 8.0Hz,4.0Hz),7.27(d,4H,J 8.0Hz),7.80(dd,2H,J 8.0Hz,3.2Hz).13C NMR(100MHz,CDCl3)δ(ppm):126.1,126.5,126.6,127.0,127.7,127.8,130.0,130.6,131.3,131.4,131.5,131.6,132.0,134.6,140.8,141.7,143.4,143.6,143.6,143.8,151.2.HR-EIMS m/z:[M]+calcd.for C62H42N2S,846.3069;found,846.3070.
实施例2(有机发光材料TPE-NTZ-B压致变色性能):
将上述所得的化合物TPE-NTZ-B在玛瑙研钵中研磨充分,与未研磨的化合物相比较,发现其红色变浅;以500nm作为激发波长,测试研磨前后的固体荧光发射光谱,结果如图1所示。研磨前的固体最大发射波长位于623nm,研磨后的固体最大发射波长蓝移至610nm。说明该有机发光材料具有压致变色性能。
实施例3(有机发光材料TPE-NTZ-TPE-1压致变色性能):
将上述所得的化合物TPE-NTZ-TPE-1在玛瑙研钵中研磨充分,与未研磨的化合物相比较,发现其颜色由橙色变为红色,变化非常明显;以506nm作为激发波长,测试研磨前后的固体荧光发射光谱,结果如图2所示。研磨前的固体最大发射波长位于598nm,研磨后的固体最大发射波长红移至612nm。说明该有机发光材料具有压致变色性能。
Claims (4)
1.一种有机发光材料在压致变色性能中的应用,其结构式如通式I所示,
其中,Ar选自芳香基或芳杂环基团,R1、R2、R3分别选自H、C1~C12烷基。
2.如权利要求1所述的应用,其特征在于:在压力作用下,固体材料的颜色和/或荧光发生改变。
3.一种有机发光材料在压致变色性能中的应用,其结构式如通式II所示,
其中,R1、R2、R3分别选自H、C1~C12烷基。
4.如权利要求3所述的应用,其特征在于:在压力作用下,固体材料的颜色和/或荧光发生改变。
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CN106349287B (zh) * | 2016-08-29 | 2018-12-21 | 四川大学 | 具有压致变色性质的季膦盐类化合物及其制备方法和应用 |
CN106671639A (zh) * | 2017-01-25 | 2017-05-17 | 上海先幻新材料科技有限公司 | 包含摩擦调制发光化合物的安全文件 |
CN107022351B (zh) * | 2017-04-28 | 2019-05-28 | 武汉工程大学 | 一种可用于生物检测的聚合物荧光材料及其制备方法 |
CN114316219B (zh) * | 2021-12-15 | 2023-11-28 | 北京大学深圳研究生院 | 兼具电致变色与热致变色性能的聚合物及其制备方法与应用 |
CN114702500B (zh) * | 2022-04-14 | 2023-10-27 | 三峡大学 | 具有压力致变色性质荧光材料及其防伪上的应用 |
CN115611721B (zh) * | 2022-09-07 | 2023-12-26 | 中国人民解放军96901部队25分队 | 一种力致荧光变色材料及其制备方法 |
CN116120259B (zh) * | 2022-12-09 | 2024-03-12 | 吉林大学 | 一种D-π-A型偶氮苯基压致变色材料及其制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101591531A (zh) * | 2009-07-02 | 2009-12-02 | 吉林大学 | 萘并噻二唑发光中心的溶液加工高效率红光电致发光材料 |
CN102942537A (zh) * | 2012-11-09 | 2013-02-27 | 浙江大学 | 一种用作pH荧光探针的苯并噻唑-苯胺类化合物及其制备方法 |
CN103102232A (zh) * | 2011-11-10 | 2013-05-15 | 三星显示有限公司 | 苯乙烯基类化合物、包含其的组合物和有机发光二极管 |
CN103804318A (zh) * | 2014-02-14 | 2014-05-21 | 中山大学 | 含三苯乙烯或四苯乙烯结构的具有聚集诱导发光性能的苯并噻唑衍生物及其制备方法和应用 |
CN104592977A (zh) * | 2013-10-31 | 2015-05-06 | 海洋王照明科技股份有限公司 | 蓝光有机电致发光材料及其制备方法和应用 |
WO2016022012A1 (fr) * | 2014-08-08 | 2016-02-11 | Moroccan Foundation For Advanced Science, Innovation & Research (Mascir) | Matériaux nano-composites fluorescents à base d'argile modifiée et applications |
Family Cites Families (1)
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US20150353515A1 (en) * | 2014-06-06 | 2015-12-10 | Wen-Hsin Huang | Novel analogs of resveratrol |
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2016
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101591531A (zh) * | 2009-07-02 | 2009-12-02 | 吉林大学 | 萘并噻二唑发光中心的溶液加工高效率红光电致发光材料 |
CN103102232A (zh) * | 2011-11-10 | 2013-05-15 | 三星显示有限公司 | 苯乙烯基类化合物、包含其的组合物和有机发光二极管 |
CN102942537A (zh) * | 2012-11-09 | 2013-02-27 | 浙江大学 | 一种用作pH荧光探针的苯并噻唑-苯胺类化合物及其制备方法 |
CN104592977A (zh) * | 2013-10-31 | 2015-05-06 | 海洋王照明科技股份有限公司 | 蓝光有机电致发光材料及其制备方法和应用 |
CN103804318A (zh) * | 2014-02-14 | 2014-05-21 | 中山大学 | 含三苯乙烯或四苯乙烯结构的具有聚集诱导发光性能的苯并噻唑衍生物及其制备方法和应用 |
WO2016022012A1 (fr) * | 2014-08-08 | 2016-02-11 | Moroccan Foundation For Advanced Science, Innovation & Research (Mascir) | Matériaux nano-composites fluorescents à base d'argile modifiée et applications |
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