CN114591340B - 苯并双七杂螺烯类圆偏振发光材料、制备方法及其应用 - Google Patents
苯并双七杂螺烯类圆偏振发光材料、制备方法及其应用 Download PDFInfo
- Publication number
- CN114591340B CN114591340B CN202210214366.3A CN202210214366A CN114591340B CN 114591340 B CN114591340 B CN 114591340B CN 202210214366 A CN202210214366 A CN 202210214366A CN 114591340 B CN114591340 B CN 114591340B
- Authority
- CN
- China
- Prior art keywords
- circularly polarized
- benzobishepta
- light
- emitting
- spiroalkene
- 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
- 239000000463 material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- 229940126062 Compound A Drugs 0.000 claims description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical group OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 claims description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000021615 conjugation Effects 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 230000031700 light absorption Effects 0.000 abstract description 3
- 125000005842 heteroatom Chemical group 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000010287 polarization Effects 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 11
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000006862 quantum yield reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- -1 polycyclic aromatic compounds Chemical class 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- YNCYPMUJDDXIRH-UHFFFAOYSA-N benzo[b]thiophene-2-boronic acid Chemical compound C1=CC=C2SC(B(O)O)=CC2=C1 YNCYPMUJDDXIRH-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001142 circular dichroism spectrum Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- UOYPNWSDSPYOSN-UHFFFAOYSA-N hexahelicene Chemical compound C1=CC=CC2=C(C=3C(=CC=C4C=CC=5C(C=34)=CC=CC=5)C=C3)C3=CC=C21 UOYPNWSDSPYOSN-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical group C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/06—Peri-condensed systems
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- 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
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- 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
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种苯并双七杂螺烯类圆偏振发光材料、制备方法及其应用。本发明提供的苯并双七杂螺烯类圆偏振发光材料,具有特殊的分子结构,其主体包括三联苯与吸电子端基,发光端基连接在中心核的四端,同时还修饰有烷链。发光端基通过稠和成芳香环的形式与三联苯中间核相连,发光基团中的杂原子的孤对电子通过大π键参与共轭,有效拓宽了共轭反应,拓宽吸光范围。同时在三联苯上引入不同的烷基链,可实现对双七螺烯材料的溶解性与结晶性的调控。本发明提供的苯并双七杂螺烯类圆偏振发光材料,具有良好的溶解性,易于加工,具有较强的发光性能及较高的不对称发光因子,是一类富有潜力的圆偏振发光的OLED材料。
Description
技术领域
本发明涉及一种螺烯类圆偏振发光材料,特别涉及一种苯并双七杂螺烯类圆偏振发光材料、制备方法及其应用,属于螺烯类圆偏振发光材料领域。
背景技术
圆偏振光在量子计算、信息防伪、三维显示、发光器件、不对称合成等多个领域有重要应用前景。获得圆偏振光的一个物理方法是由线偏振光经过1/4波片转换而来。相比较,化学方法通过发光材料与手性的有效耦合直接产生圆偏振发光,避免了物理方法中通过滤光片引起的能量损耗,并为新型柔性和微型器件的研制提供了有利条件,成为近年来化学以及多学科交叉研究的一个前沿方向,引起广泛关注。
螺烯是一类通过多个芳香环在其邻位按一定扭曲角度连续稠合形成的具有螺旋手性的非平面多环芳烃化合物。经过几十年的发展,螺烯类圆偏振发光材料的两个重要性能参数:不对称发光因子(glum)和荧光量子产率(PLQY)分别可以达到0.028和19%【J.Am.Chem.Soc.2014,136,15,5555–5558】,因此螺烯类衍生物被认为是一种极具发展前景的圆偏振发光材料而受到广泛关注。
现有技术中,虽然螺烯类圆偏振发光材料取得较大的进展,但是圆偏振发光响应强的高级螺烯普遍存在合成路线复杂,合成产率低,荧光量子产率和不对称发光因子相对低的问题。因此,亟需开发出一种新型螺烯类圆偏振发光材料,以解决上述问题。
发明内容
针对现有技术中圆偏振发光响应强的高级螺烯普遍存在合成路线复杂,合成产率低,荧光量子产率和不对称发光因子相对低的问题,本发明的第一个目的是在于提供一种荧光量子产率高,不对称发光因子较高的苯并双七杂螺烯类圆偏振发光材料。
本发明的第二个目的是在于提供一种条件温和,合成路线简单,产率高的制备苯并双七杂螺烯类圆偏振发光材料的方法。
本发明的第三个目的在于提供苯并双七杂螺烯类圆偏振发光材料在OLED中的应用,基于CPL材料的圆偏振有机发光二极管(CP-OLED)可以发出与偏振片具有同手性的圆偏振光,提高了能量利用率。
为了实现上述技术目的,本发明提供了一种苯并双七杂螺烯类圆偏振发光材料,具有式1结构:
其中,
R为C1~C20的烷基;
Ar为以下基团中任意一种:(虚线处为连接位置)
本发明还提供所述苯并双七杂螺烯类圆偏振发光材料的制备方法,包括以下步骤:
(1)化合物A和发光端基-Ar通过钯催化偶联反应得到化合物B;
所述发光端基-Ar为以下任意一种:
(2)化合物B通过Scholl反应氧化脱氢关环,得到目标产物TM:
优选的方案,步骤(1)中,钯催化偶联反应的条件为:
溶剂为1,4-二氧六环和水,或者1,4-二氧六环和甲苯;
催化剂为四三苯基膦钯,或者Pd2(dba)3和2-双环己基膦-2',6'-二甲氧基联苯(S-Phos)。
优选的方案,步骤(1)中,化合物A与发光端基-Ar的摩尔比为1:7~9,在80~100℃温度下回流反应12~24小时。
优选的方案,步骤(2)中,Scholl反应的条件为:溶剂为超干二氯甲烷,催化剂为三氟甲基磺酸。
优选的方案,步骤(2)中,化合物B与2,3-二氯-5,6-二氰对苯醌(DDQ)的摩尔比为1:4~12;在0~20℃温度下反应2~24小时。
本发明还提供所述苯并双七杂螺烯类圆偏振发光材料的应用,将其作为圆偏振发光材料应用于发光二极管器件。
相对于现有技术,本发明技术方案具有以下有益效果:
本发明提供的苯并双七杂螺烯类圆偏振发光材料,具有特殊的分子结构,其主体包括三联苯与吸电子端基,发光端基连接在中心核的四端,同时还修饰有烷基链。发光端基通过稠和成芳香环的形式与三联苯中间核相连,发光基团中的杂原子的孤对电子通过大π键参与共轭,有效拓宽了共轭反应,拓宽吸光范围。同时在三联苯上引入不同的烷基链,可实现对双七螺烯材料的溶解性与结晶性的调控。
本发明提供的苯并双七杂螺烯类圆偏振发光材料,具有良好的溶解性,易于加工,具有较强的发光性能(PLQY≥90%)及较高的不对称发光因子(glum≥10-3),是一类富有潜力的圆偏振发光材料。
本发明提供的苯并双七杂螺烯类圆偏振发光材料,与之前的低级螺烯材料相比,此X形状的双七螺烯有较高的稳定性,可以通过发光端基调控发光范围,具有很高的吸光系数,易于加工,其成品可以制成柔性OLED。
本发明所述苯并双七杂螺烯类圆偏振发光材料的制备方法,合成条件温和、路线简单,价格低廉,有利于实现大规模生产。
附图说明
【图1】为实施例1制备得到的圆偏振发光材料D7H-TAZ的合成路线图。
【图2】为实施例1制备得到的圆偏振发光材料D7H-TAZ的1HNMR。
【图3】为实施例1制备得到的圆偏振发光材料D7H-TAZ的13CNMR。
【图4】为实施例1制备得到的圆偏振发光材料D7H-TAZ在氯仿溶液中的吸收谱图和荧光谱图。
【图5】为实施例1制备圆偏振发光材料D7H-TAZ的CD图。
【图6】为实施例1制备圆偏振发光材料D7H-TAZ的CPL图。
【图7】为实施例2制备得到的圆偏振发光材料D7H-BT的合成路线图。
【图8】为实施例2制备得到的圆偏振发光材料D7H-BT的1HNMR。
【图9】为实施例2制备得到的圆偏振发光材料D7H-BT的13CNMR。
【图10】为实施例2制备得到的圆偏振发光材料D7H-BT在氯仿溶液中的吸收谱图和荧光谱图。
【图11】为实施例2制备圆偏振发光材料D7H-BT的CD图。
【图12】为实施例2制备圆偏振发光材料D7H-BT的CPL图。
具体实施方式
下面通过具体实验方式来进一步说明本发明的技术方案。
下述实施例中所述实验方法,如无特殊说明,均为常规方法,所述试剂和材料,如无特殊说明,均可从商业途径获得。
实施例1
上述所述的R为Ar为/>时,如图1所示,苯并双七杂螺烯类圆偏振发光材料的合成路线如下:
(1)化合物B由化合物A通过Suzuki偶联反应得到;
化合物B的合成:
在反应瓶中依次加入2-甲基-5-(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊烷-2-基)-2H-苯并[d][1,2,3]三唑(2.57g,9.49mmol),化合物A(0.8g,1.22mmol),碳酸钾(2.59g,18.78mmol)和催化剂Pd(PPh3)4(0.1756g,0.152mmol),反复充放氩气三次,分别取84ml 1,4-二氧六环和12ml H2O配制为混合溶液,向其鼓氩气30分钟,然后用注射器加入反应瓶中,反应液加热到100℃搅拌1天,待反应冷却至室温,将其倒入水中,用二氯甲烷反复萃取,有机溶剂通过旋转蒸发去除,粗产品通过硅胶柱分离提纯,以二氯甲烷:乙酸乙酯(20:1)为洗脱剂,得到白色固体产物(1.05g),即为化合物B,化合物B的产率为98%;
(2)化合物B和DDQ通过Scholl反应得到D7H-TAZ材料:
圆偏振发光材料D7H-BTZ的合成:在装有195ml的超干二氯甲烷(DCM)的反应瓶中依次加入化合物B(300mg,0.34mmol)和2,3-二氯-5,6-二氰对苯醌DDQ(786mg,3.462mmol),向混合溶液鼓氩气30分钟,然后将三口烧瓶置于0℃下搅拌10分钟,再向其加入5.17ml三氟甲基磺酸(TfOH),然后将反应混合溶液提至室温搅拌过夜,待反应完毕,加入三乙胺溶液使其调至中性,然后将反应混合液倒入水中,反复用二氯甲烷萃取多次,有机溶剂通过旋转蒸发除去,粗产品通过硅胶柱分离提纯,以二氯甲烷:乙酸乙酯(20:1)作为洗脱剂,得到橘黄色固体产物(172mg)即为D7H-TAZ。
目标产物D7H-TAZ的产率58.8%,如图2和图3所示,D7H-TAZ的核磁谱图为1HNMR(400MHz,CDCl3)δ9.37(s,4H),9.08(d,J=9.3Hz,4H),8.02(d,J=9.2Hz,4H),3.86(s,12H),1.86(s,18H)。13C NMR(101MHz,CDCl3)δ149.25,143.03,142.93,130.85,127.11,124.48,123.85,123.50,121.75,120.68,119.99,116.26,42.36,35.97,32.17。
图4为D7H-TAZ在二氯甲烷溶液中的吸收谱图和荧光谱图,由图4可以看出D7H-TAZ在486nm和514nm处有两个很强的吸收峰,D7H-TAZ的荧光发射峰在550nm处,斯托克位移较小,表明其在基态和激发态的结构变化较小。
图5为D7H-TAZ的CD图,由图5可以看出D7H-TAZ的两个异构体在316nm和365nm展现了最强的科顿效应。
图6为D7H-TAZ的CPL图,由图6可以看出D7H-TAZ在最大发射峰处有很明显手性信号。
实施例2
上述所述的R为Ar为/>时,如图7所示,苯并双七杂螺烯类圆偏振发光材料的合成路线如下:
(1)化合物B’由化合物A’通过Suzuki偶联反应得到;
在反应瓶中依次加入发光基团苯并噻吩-2-硼酸(1.08g,6.08mmol),化合物A’(0.5g,0.760mmol),碳酸钾(1.62g,11.7mmol)和催化剂Pd2(dba)3(0.112g,0.152mmol),2-双环己基膦-2',6'-二甲氧基联苯(200.6mg,0.48mmol)反复充放氩气三次,分别取84ml 1,4-二氧六环和12ml H2O配制为混合溶液,向其鼓氩气30分钟,然后用注射器加入反应瓶中,反应液加热到100℃搅拌1天,待反应冷却至室温,将其倒入水中,用二氯甲烷反复萃取,有机溶剂通过旋转蒸发去除,粗产品通过硅胶柱分离提纯,以二氯甲烷:石油醚(1:4)为洗脱剂,得到白色固体产物(0.595g),即为化合物B’,化合物B’的产率为90%;
(2)圆偏振发光材料D7H-BT由化合物B’通过Scholl反应得到;
圆偏振发光材料D7H-BT的合成:在氩气条件下,将化合物B’(500mg,0.573mmol)和2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)(601mg,2.65mmol)溶解在150mL超干二氯甲烷中,将所得溶液冷却至0℃,然后滴加三氟甲磺酸(1.5mL)。0℃下搅拌2小时后,反应混合物依次用三乙胺中和,二氯甲烷稀释,水洗,得到的有机相用Na2SO4干燥后旋干,然后通过硅胶柱色谱法纯化,用二氯甲烷/己烷(4/1)作为洗脱剂,得到橙色粉末(322mg),即为产物D7H-BT。
D7H-BT的产率为65%,如图8和图9所示,核磁谱为1H NMR(400MHz,CD2Cl2)δ9.19(s,4H),7.82(dd,J=6.9,1.2Hz,4H),7.75(dd,J=7.3,1.2Hz,4H),7.42–7.24(m,8H),1.72(s,18H);13C NMR(101MHz,CDCl3,298K,ppm)δ150.66,138.22,138.13,136.01,131.53,128.89,125.29,124.24,123.72,123.43,122.11,121.03,119.89,119.42,35.83,31.74.
图10为D7H-BT在二氯甲烷溶液中的吸收谱图和荧光谱图,由图10可以看出D7H-BT在483nm和521nm处有两个很强的吸收峰,D7H-BT的荧光发射峰在562nm处,整体比D7H-TAZ红移,但斯托克位移也较小,表明其在基态和激发态的结构变化也较小。
图11为D7H-BT的CD图,由图11可以看出D7H-BT的两个异构体的CD谱图是镜像对称的,都在在330nm和388nm展现了最强的科顿效应。
图12为D7H-TAZ的CPL图,由图12可以看出D7H-BT在最大发射峰处有很明显手性信号。
表1列出了两个圆偏振发光材料D7H-BT和D7H-TAZ的手性光学性能参数。
表1
PLQY | gabs | gcpl | |
D7H-BT | 46.2% | 1.4×10-2 | 1.2×10-3 |
D7H-TAZ | 96.5% | 2.5×10-2 | 1.2×10-3 |
本发明公开了一种苯并双七杂螺烯类圆偏振发光材料、制备方法及其应用。该螺烯类圆偏振发光分子材料包括靴二蒽中心核和二元芳杂环,二元芳杂环稠合在中心核的四端,其制备过程为以2,2”,6,6”-四溴-1,1':4',1”-三联苯中心核为原料,通过钯催化偶联反应引入二元芳杂环,然后通过分子内Scholl反应环氧化脱氢得到目标产物。该类圆偏振发光材料具有较高的荧光量子产率和发光不对称因子,有望制备高效率发光器件。
Claims (7)
1.一种苯并双七杂螺烯类圆偏振发光材料,其特征在于,具有式1结构:
其中,
R为
Ar为以下基团,虚线处为连接位置,Ar基团均相同,1、2表示连接位点:
2.根据权利要求1所述苯并双七杂螺烯类圆偏振发光材料的制备方法,其特征在于,包括以下步骤:
(1)化合物A和发光端基-Ar通过钯催化偶联反应得到化合物B;
发光端基-Ar为或者/>
R为
(2)化合物B通过Scholl反应氧化脱氢关环,得到目标产物TM:
3.根据权利要求2所述苯并双七杂螺烯类圆偏振发光材料的制备方法,其特征在于,步骤(1)中,钯催化偶联反应的条件为:
溶剂为1,4-二氧六环和水,或者甲苯;
催化剂为Pd(PPh3)4,或者Pd2(dba)3和S-Phos。
4.根据权利要求2所述苯并双七杂螺烯类圆偏振发光材料的制备方法,其特征在于,步骤(1)中,化合物A与发光端基-Ar的摩尔比为1:7~9,在80~100℃温度下回流反应12~24小时。
5.根据权利要求2所述苯并双七杂螺烯类圆偏振发光材料的制备方法,其特征在于,步骤(2)中,Scholl反应的条件为:溶剂为超干二氯甲烷,催化剂为三氟甲基磺酸。
6.根据权利要求2所述苯并双七杂螺烯类圆偏振发光材料的制备方法,其特征在于,步骤(2)中,化合物B与DDQ的摩尔比为1:4~12;在0~20℃温度下反应2~24小时。
7.根据权利要求1所述苯并双七杂螺烯类圆偏振发光材料的应用,将其作为圆偏振发光材料应用于发光二极管器件。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210214366.3A CN114591340B (zh) | 2022-03-07 | 2022-03-07 | 苯并双七杂螺烯类圆偏振发光材料、制备方法及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210214366.3A CN114591340B (zh) | 2022-03-07 | 2022-03-07 | 苯并双七杂螺烯类圆偏振发光材料、制备方法及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114591340A CN114591340A (zh) | 2022-06-07 |
CN114591340B true CN114591340B (zh) | 2023-08-11 |
Family
ID=81807925
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210214366.3A Active CN114591340B (zh) | 2022-03-07 | 2022-03-07 | 苯并双七杂螺烯类圆偏振发光材料、制备方法及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114591340B (zh) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150184068A1 (en) * | 2012-07-27 | 2015-07-02 | Imperial Innovations Limited | Electroluminescent compositions |
CN106008318A (zh) * | 2016-05-19 | 2016-10-12 | 中国科学院化学研究所 | 一种具有圆偏振发光性质的手性有机染料分子及其制备方法与应用 |
CN110398300A (zh) * | 2019-06-24 | 2019-11-01 | 中北大学 | 一种基于集群nv色心金刚石的温度传感器 |
US20200354294A1 (en) * | 2019-05-06 | 2020-11-12 | University Of Wyoming | Syntheses, characterizations, and applications of heli-acenes |
CN113121511A (zh) * | 2020-01-15 | 2021-07-16 | 华南理工大学 | 一类具有圆偏振发光的菲并咪唑电致发光材料及其制备方法与应用 |
-
2022
- 2022-03-07 CN CN202210214366.3A patent/CN114591340B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150184068A1 (en) * | 2012-07-27 | 2015-07-02 | Imperial Innovations Limited | Electroluminescent compositions |
CN106008318A (zh) * | 2016-05-19 | 2016-10-12 | 中国科学院化学研究所 | 一种具有圆偏振发光性质的手性有机染料分子及其制备方法与应用 |
US20200354294A1 (en) * | 2019-05-06 | 2020-11-12 | University Of Wyoming | Syntheses, characterizations, and applications of heli-acenes |
CN110398300A (zh) * | 2019-06-24 | 2019-11-01 | 中北大学 | 一种基于集群nv色心金刚石的温度传感器 |
CN113121511A (zh) * | 2020-01-15 | 2021-07-16 | 华南理工大学 | 一类具有圆偏振发光的菲并咪唑电致发光材料及其制备方法与应用 |
Non-Patent Citations (1)
Title |
---|
含咔唑基团芘类荧光材料的合成与发光性质;黄诚等,;《精细化工》(第01期);第1-5页 * |
Also Published As
Publication number | Publication date |
---|---|
CN114591340A (zh) | 2022-06-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110240699B (zh) | 一类具有圆偏振发光性能的侧链型液晶聚合物及其制备方法 | |
CN112300201B (zh) | 一种三聚茚基香豆素-咔咯-卟啉四元体系星型化合物的合成及其制备方法 | |
CN109593095B (zh) | X型杂稠苝芳烃的双螺烯功能分子材料及其制备和应用 | |
CN109096313B (zh) | 一种三聚茚基咔咯-卟啉-富勒烯星型化合物的制备方法 | |
CN114105955A (zh) | 一种芴螺三苯胺衍生化合物及其制备方法和应用 | |
CN103214521A (zh) | 一种制备二苯并磷杂环戊二烯衍生物的方法 | |
CN114591340B (zh) | 苯并双七杂螺烯类圆偏振发光材料、制备方法及其应用 | |
CN112442054B (zh) | 一种三聚茚基咔咯-卟啉-bodipy星型化合物的制备方法 | |
CN107001926B (zh) | 双(二芳基亚甲基)-二氢并苯类化合物的聚集诱导发光和聚集促进光致变色 | |
CN111825645A (zh) | 一类萘并香豆素化合物和制备方法及其作为光致发光材料的应用 | |
CN114507237B (zh) | 基于二苊并吡嗪并喔啉的氮杂多环稠环化合物及合成方法 | |
CN102050782A (zh) | 螺芴吖啶中间体的制备方法 | |
CN116507598A (zh) | 用于制备氘化蒽化合物的方法、反应组合物、氘化蒽化合物和组合物 | |
CN116547255A (zh) | 用于制备氘化蒽化合物的方法、反应组合物、氘化蒽化合物和组合物 | |
CN112299982B (zh) | 一种基于三蝶烯的线性并苯类化合物及其合成与应用 | |
CN110746462A (zh) | 一种树枝状环三磷腈化合物的高效合成方法 | |
CN114656474B (zh) | 基于萘二酰亚胺的共轭大环材料及其制备方法 | |
CN108047087A (zh) | 3’-(4-溴萘-1-基)[1,1’-联苯基]-4-腈及其合成方法 | |
CN115819281B (zh) | 一种氰基取代的对苯撑乙烯衍生物、制备方法及应用 | |
CN114409672B (zh) | 一类基于苯并二噻吩的共轭大环材料及其制备方法和应用 | |
CN115057762B (zh) | 抗聚集诱导猝灭型刚性Gemini荧光两亲分子及其合成方法 | |
CN116987107A (zh) | 一种芳基硼氮类窄谱带蓝光化合物及其制备方法和应用 | |
CN111423595B (zh) | 一种基于螺芴四位点柱[n]芳烃的三维超分子聚合物及其制备方法与应用 | |
CN117964651A (zh) | 一种窄谱带圆偏振发光分子及其制备方法和应用 | |
CN117903002A (zh) | 基于四苯乙烯功能化的二氰基乙烯、其制备方法及其应用和无墨书写材料 |
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 |