CN116162114A - 一种圆偏振发光配合物材料及其应用 - Google Patents
一种圆偏振发光配合物材料及其应用 Download PDFInfo
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- CN116162114A CN116162114A CN202310232188.1A CN202310232188A CN116162114A CN 116162114 A CN116162114 A CN 116162114A CN 202310232188 A CN202310232188 A CN 202310232188A CN 116162114 A CN116162114 A CN 116162114A
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- 239000011365 complex material Substances 0.000 title claims abstract description 45
- 230000010287 polarization Effects 0.000 title abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 13
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052763 palladium Chemical group 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
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- 239000003446 ligand Substances 0.000 abstract description 4
- 125000003003 spiro group Chemical group 0.000 abstract description 3
- 230000001815 facial effect Effects 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 68
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 60
- 238000006243 chemical reaction Methods 0.000 description 60
- 239000012043 crude product Substances 0.000 description 51
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 42
- 238000004440 column chromatography Methods 0.000 description 41
- 238000002360 preparation method Methods 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- 229910052786 argon Inorganic materials 0.000 description 34
- 239000012044 organic layer Substances 0.000 description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 239000007787 solid Substances 0.000 description 28
- 238000001816 cooling Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
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- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 11
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 11
- 229910052700 potassium Inorganic materials 0.000 description 11
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- 238000000926 separation method Methods 0.000 description 11
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- 239000000843 powder Substances 0.000 description 10
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- 238000011049 filling Methods 0.000 description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 8
- -1 tris (t-butylphosphorus) tetrafluoroborate Chemical compound 0.000 description 8
- 238000004296 chiral HPLC Methods 0.000 description 7
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- 238000003756 stirring Methods 0.000 description 6
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- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 230000006340 racemization Effects 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000005036 potential barrier Methods 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 2
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- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- KQZLRWGGWXJPOS-NLFPWZOASA-N 1-[(1R)-1-(2,4-dichlorophenyl)ethyl]-6-[(4S,5R)-4-[(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]-5-methylcyclohexen-1-yl]pyrazolo[3,4-b]pyrazine-3-carbonitrile Chemical compound ClC1=C(C=CC(=C1)Cl)[C@@H](C)N1N=C(C=2C1=NC(=CN=2)C1=CC[C@@H]([C@@H](C1)C)N1[C@@H](CCC1)CO)C#N KQZLRWGGWXJPOS-NLFPWZOASA-N 0.000 description 2
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 2
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- FQMZXMVHHKXGTM-UHFFFAOYSA-N 2-(1-adamantyl)-n-[2-[2-(2-hydroxyethylamino)ethylamino]quinolin-5-yl]acetamide Chemical compound C1C(C2)CC(C3)CC2CC13CC(=O)NC1=CC=CC2=NC(NCCNCCO)=CC=C21 FQMZXMVHHKXGTM-UHFFFAOYSA-N 0.000 description 2
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 2
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- 229940126657 Compound 17 Drugs 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 2
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
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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
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- C—CHEMISTRY; METALLURGY
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- 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
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Abstract
Description
技术领域
本发明属于有机发光材料领域,具体涉及一种圆偏振发光配合物材料及其应用。
背景技术
近些年来,具有圆偏振发光(Circularly Polarized Luminescence)的手性光学功能材料因其在三维光学显示、信息加密传输和存储、生物编码、光电器件等方面的广泛潜在应用而受到越来越多的关注。在开发CPL材料时,一个关键问题是获得高发光不对称因子(glum),为了便于量化CPL,通常用公式glum=2×(IL-IR)/(IL+IR)进行计算,其中IL和IR分别是左/右旋圆偏振光发射强度。|glum|的最大值为2,表示完全的左或右旋圆偏振光。尽管目前最高的glum来自手性镧系金属配合物,然而这些材料在某些方面如其电致发光器件表现非常小发光效率,因此,科学家们将研究兴趣逐渐放到开发具有CPL活性的过渡金属配合物和有机小分子上。
一般地,新型圆偏振发光材料的设计策略主要通过在发色团上通过共价键或者配位键引入手性单元,然后通过手性传递实现圆偏振发光。然而通过这种策略构筑的手性分子大都呈现较弱的CPL信号,且手性源的种类收到限制。为了提高CPL信号,有研究学者证明利用超分子自组装可以将苝-双酰亚胺体系的|glum|值从0.003提高到0.008,尽管这种策略可以有效地提高CPL信号,但是,一般条件下,不仅用于自组装的材料比较难选择,而且实现自组装过程也比较苛刻,通常需要精确地控制多相之间的比例,以及所需的溶剂、浓度、温度等外界条件,且不适于制备OLED器件。
发明内容
因此,本发明要解决的技术问题在于现有技术中手性源的种类收到限制,消旋势垒低的缺陷,从而提供一种圆偏振发光配合物材料及其应用。
为此,本发明采用如下技术方案:
本发明提供一种圆偏振发光配合物材料,所述圆偏振发光配合物材料包括式Ⅰ表示的化合物:
其中,M为铂或钯;
A、B、C和D各自独立的选自氮或卡宾碳原子;
环L1、环L2、环L3以及环L4各自独立选自多元芳环、芳香杂环、具有一个或多个取代基的芳环或芳香杂环,所述取代基各自独立选自H、D、F、Cl、Br、I、-CN、-NO2、-CF3、-OH、-SH、-NH、-NH2、C1-C30的直连烷烃、C3-C30的支链烷烃、C3-C30的环烷基、C1-C30的烷氧基/烷巯基、C6-C60的芳基/杂芳基/醚基/芳杂醚基;其中,杂芳基的杂原子可以独立选自Si、Ge、N、P、O、S、Se;
环L1、环L2、环L3以及环L4均没有手性,或及易消旋,不足以满足手性应用,或环L1、环L2、环L3以及环L4自带的手性中心与本发明所构造的手性中心无关。
进一步地,式Ⅰ表示的化合物包括如下结构:
其中,键连结构X和Y为连接芳环或芳香杂环的原子或基团,各自独立的选自-C-、-N-、-Si-、-S-、芳香环或芳香杂环、具有一个或多个取代基的芳环或芳香杂环;
其中,所述取代基各自独立选自H、D、F、Cl、Br、I、-CN、-NO2、-CF3、-OH、-SH、-NH、-NH2、C1-C30的直连烷烃、C3-C30的支链烷烃、C3-C30的环烷基、C1-C30的烷氧基/烷巯基、C6-C60的芳基/杂芳基/醚基/芳杂醚基;其中,杂芳基的杂原子可以独立选自Si、Ge、N、P、O、S、Se。
M与环L1、L2、L3或L4中的任意两个或两个以上的环选用如下配位方式构筑手性中心
X和Y各自独立选自如下键连结构:
式I表示的化合物具有化学式1-1至化学式11-39任一所示结构:
上述圆偏振发光配合物材料的制备方法为以非手性化合物为原料,在有机合成中构造新的手性中心,实现分子的手性性质,具体的,通过金属配位,将原本可以自由转动的结构锚定,结合位阻效应,使目标化合物产生对映异构体,再通过手性制备的方式拆分对映异构体,获得手性化合物,具体包括螺手性、轴手性和面手性等配合物。
本发明还提供上述圆偏振发光配合物材料的应用,应用于手性药物、手性农药、手性液晶材料、手性导电聚合物材料、手性介孔材料、手性纳米材料和手性电致发光材料。
本发明技术方案,具有如下优点:
(1)本发明的圆偏振发光配合物材料,其手性与使用的材料本身无关,通过配位驱动螺手性或轴手性圆偏振发光材料,具有手性来源广、不对称因子高、发光性能好、热稳定性好等特点。本发明通过设计不同类型的配体,可以构筑不同螺手性、轴手性、面手性圆偏振配合物,并将其作为不同的运用。
(2)本发明通过配位诱导大位阻产生螺手性、轴手性、面手性,所设计的配体不含手性中心,不受制于手性原料的种类,在分子设计上更加自由,本发明所设计分子空间位阻较大,且分子骨架全部为共轭架构,刚性较强,分子不能呈平面构型且因大位阻而具备较大的消旋势垒,(在如实施例1-1、1-7、1-12、1-14和1-15的制备中包括高温下升华的操作而不发生消旋,说明消旋势垒较大),高温等极端条件依然能保持手性性能,使配位不能呈平面而产生螺旋手性。同时,大位阻使得配合物分子整体呈空间立体构型,能有效抑制分子间的聚集,获得较好的电致发光性能。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案,下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图是本发明的一些实施方式,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为实施例1手性HPLC测试效果图;
图2为实施例3手性HPLC测试效果图;
图3为实施例4手性HPLC测试效果图;
图4为实施例12手性HPLC测试效果图;
图5为实施例1制备前手性HPLC测试效果图;
图6为实施例1制备后峰1手性HPLC测试效果图;
图7为实施例1制备后峰2手性HPLC测试效果图;
图8为实施例1经手性拆分后两组分的圆二色普吸收图;
图9为实施例1经手性拆分后两组分在二氯甲烷溶液中的圆偏振发光光谱图;
图10为实施例1经手性拆分后两组分在二氯甲烷溶液中不对称因子测试图;
图11为实施例1经手性拆分后两组分在纯膜状态下的圆偏振发光光谱图;
图12为实施例1经手性拆分后两组分在纯膜状态下不对称因子测试图。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明,并不局限于所述最佳实施方式,不对本发明的内容和保护范围构成限制,任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品,均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者,按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。
以下具体实施例是对本发明的进一步说明,所举案例并不能列举出本发明的全部实施方式,仅以其中部分实施方式为例进行说明,具体实施例如下:
实施例1
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)将化合物1(1g,4.69mmol)、化合物2(734mg,4.69mmol)和四三苯基膦钯(228mg)加入100mL的圆底两口瓶中,抽真空充氩气反复三次,再依次注入甲苯(40mL)、乙醇(10mL)和3.5M的碳酸钾水溶液(10mL)。85℃下反应20小时。冷却,反应液用二氯甲烷和水萃取,收集下层,减压蒸馏除去溶剂。粗产品经柱层析分离提纯,得到白色固体1.2g,即化合物3,产率89%。1H NMR(400MHz,Chloroform-d)δ9.47(d,J=8.1Hz,1H),8.36(t,J=1.9Hz,1H),8.27–8.15(m,2H),7.97(d,J=8.3Hz,1H),7.94–7.88(m,1H),7.84–7.66(m,4H),7.52–7.41(m,2H).
(2)将化合物3(1.1g,3.81mmol),3,5-二叔丁基苯胺(390mg,1.9mmol),醋酸钯(40mg),三(叔丁基磷)四氟硼酸盐(230mg),叔丁醇钠(1.10g)和重蒸甲苯(30mL)加入到100mL的圆底烧瓶中,抽真空充氩气反复3次。130℃下反应24小时。冷却至室温后用二氯甲烷和水萃取,收集有机层。减压蒸馏除去有机溶剂。粗产品经柱层析过柱分离,得到白色产品1.1g,即化合物4,产率81%。1H NMR(400MHz,Chloroform-d)δ9.35–9.28(m,2H),8.21–8.13(m,4H),8.02(dt,J=7.7,1.3Hz,2H),7.92(d,J=8.4Hz,2H),7.89–7.83(m,2H),7.76(d,J=8.8Hz,2H),7.69–7.59(m,6H),7.47(t,J=7.9Hz,2H),7.35–7.30(m,2H),7.21(dd,J=15.6,1.8Hz,3H),7.06(s,1H),1.30(s,18H).
(3)将化合物4(500mg,0.7mmol),氯亚铂酸钾(321mg,0.77mmol)和醋酸(40mL)加入至100mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应48小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到暗红色产品330mg,即圆偏振发光配合物材料1-1,产率52%。1H NMR(400MHz,Chloroform-d)δ9.65(d,J=8.3Hz,2H),8.17(d,J=8.4Hz,2H),8.03(d,J=8.3Hz,2H),7.58(t,J=1.8Hz,1H),7.56(d,J=7.4Hz,2H),7.39–7.31(m,4H),7.24(s,2H),7.19(dd,J=8.3,7.4Hz,2H),7.12(d,J=8.7Hz,2H),7.05(ddd,J=8.0,6.9,1.2Hz,2H),6.54(ddd,J=8.3,7.0,1.3Hz,2H),6.42(d,J=8.3Hz,2H),1.40(s,18H).
实施例2:
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)将5(7g,20.6mmol),1-溴喹啉(4.3,20.6mmol),和四三苯基膦钯(238m g)加入100mL的圆底两口瓶中,抽真空充氩气反复三次,再依次注入甲苯(150mL)、乙醇(50mL)和2M的碳酸钾水溶液(50mL)。85℃下反应20小时。冷却,反应液用二氯甲烷和水萃取,收集下层,减压蒸馏除去溶剂。粗产品经柱层析分离提纯,得到白色固体5.1g,即化合物6,产率73%。1H NMR(400MHz,Chloroform-d),δ(ppm):8.18(s,1H),8.16(s,1H),8.11(t,J=1.7Hz,1H),8.09(t,J=1.7Hz,1H),7.79(s,1H),7.77(s,1H),7.71(t,J=7.7Hz,1H),7.61(t,J=1.9Hz,1H),7.50(t,J=7.0Hz,1H),1.39(s,9H).
(2)将化合物6(1.5g,4.4mmol),3,5-二叔丁基苯胺(0.45,2.2mmol),醋酸钯(25mg),三(叔丁基磷)四氟硼酸盐(100mg),叔丁醇钠(0.43g,4.4mmol)和重蒸甲苯(50mL)加入到100mL的圆底烧瓶中,抽真空充氩气反复3次。130℃下反应24小时。冷却至室温后用二氯甲烷和水萃取,收集有机层。减压蒸馏除去有机溶剂。粗产品经柱层析过柱分离,得到白色产品1.3g,即化合物7,产率81%。1H NMR(400MHz,Chloroform-d),δ(ppm):8.15–8.09(m,4H),7.84(t,J=1.7Hz,2H),7.80–7.75(m,2H),7.73–7.66(m,6H),7.48(ddd,J=8.1,6.9,1.2Hz,2H),7.34(t,J=1.9Hz,2H),7.08(s,3H),1.35(s,18H),1.26(s,18H).13C NMR(101MHz,Chloroform-d),δ(ppm):158.16,152.62,151.42,148.27,148.18,146.95,140.39,136.54,129.76,129.46,127.39,127.10,126.08,122.72,120.46,119.62,118.82,118.70,116.61,35.06,34.96,31.49,31.41.
(3)将化合物7(1g,1.4mmol),氯亚铂酸钾(0.7g,1.7mmol)和醋酸(40mL)加入至100mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应48小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到暗红色产品900mg,即圆偏振发光配合物材料1-7,产率70%。1H NMR(400MHz,DMSO-d6),δ(ppm):8.72(d,J=8.8Hz,2H),8.58(d,J=8.9Hz,2H),8.10(dd,J=8.2,1.4Hz,2H),7.83–7.73(m,4H),7.64(t,J=1.8Hz,1H),7.46(t,J=7.5Hz,2H),7.17(d,J=1.8Hz,2H),6.99(ddd,J=8.5,6.8,1.4Hz,2H),6.43(d,J=1.6Hz,2H),1.41(s,18H),1.23(s,18H).MALDI-MS(m/z)calcd for C52H55N3Pt·[M]+:917.11.Found:917.37.Analy.Calcl.for C52H55N3Pt·H2O:C,66.79;H;6.14;N,4.49;found:C,67.12,H,6.77,N,4.46.
实施例3:
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)将化合物8(5.15g,42.2mmol),化合物9(10g,42.2mmol)和四三苯基膦钯(500mg,0.43mmol)加入500mL的圆底烧瓶中,再依次注入甲苯(60mL)、乙醇(20mL)和2M的碳酸钾水溶液(20mL),抽真空充氩气反复三次。85℃下反应12小时。冷却,反应液用二氯甲烷和水萃取,收集下层,减压蒸馏除去溶剂。粗产品经柱层析分离提纯,得到黄色油状产品9.3g,即化合物10,产率95%。1H NMR(500MHz,Chloroform-d)δ8.11(d,J=8.5Hz,1H),7.58–7.55(m,2H),7.48(t,J=7.7Hz,3H),7.44(d,J=8.5Hz,1H).
(2)将化合物10(9.0g,38.5mmol)和三苯基膦(50.4g,192.3mmol)加入250mL的圆底两口瓶中,抽真空充氩气反复三次,再注入邻二氯苯(100ml)。85℃下反应12小时。冷却,反应液用二氯甲烷和水萃取,收集下层,减压蒸馏除去溶剂。粗产品经柱层析分离提纯,得到淡黄色粉末产品3.5g,即化合物11,产率46%。1H NMR(400MHz,Chloroform-d)δ8.36(dd,J=7.9,1.0Hz,1H),8.20(s,1H),7.70(d,J=8.5Hz,1H),7.54(ddd,J=8.2,7.0,1.2Hz,1H),7.47(dt,J=8.2,1.0Hz,1H),7.36–7.34(m,1H),7.34–7.32(m,1H).
(3)将化合物11(3.5g,17.3mmol)、碘苯(5.3g,26mmol)、碘化亚铜(986mg,5.2mmol)、左旋-反式-1,2-环己二胺(591mg,5.2mmol)、磷酸钾(7.33g,34.6mmol)加入250mL的圆底两口瓶中,抽真空充氩气反复三次,再注入1,4-二氧六环(100ml)。110℃下反应12小时。冷却,反应液用二氯甲烷和水萃取,收集下层,减压蒸馏除去溶剂。粗产品经柱层析分离提纯,得到白色粉末产品3.8g,即化合物12,产率80%。1H NMR(500MHz,Chloroform-d)δ8.44(dd,J=7.9,1.0Hz,1H),7.67–7.61(m,3H),7.55–7.51(m,4H),7.45(d,J=8.3Hz,1H),7.40–7.36(m,1H),7.33(d,J=8.5Hz,1H).
(4)将化合物12(1.2g,4.3mmol),间溴苯硼酸(673.4mg,4.3mmol)和四三苯基膦钯(250mg,0.2mmol)加入100mL的圆底烧瓶中,再依次注入甲苯(26mL)、乙醇(9mL)和2M的碳酸钾水溶液(9mL),抽真空充氩气反复三次。85℃下反应12小时。冷却,反应液用二氯甲烷和水萃取,收集下层,减压蒸馏除去溶剂。粗产品经柱层析分离提纯,得到白色粉末产品1.2g,即化合物13,产率85%。1H NMR(400MHz,Chloroform-d)δ8.56(d,J=7.8Hz,1H),8.20(t,J=1.8Hz,1H),8.03(dt,J=7.7,1.4Hz,1H),7.76(s,2H),7.65(t,J=7.7Hz,2H),7.60–7.55(m,2H),7.54–7.50(m,2H),7.48(d,J=8.2Hz,1H),7.46–7.41(m,1H),7.38(tt,J=8.0,1.4Hz,2H).
(5)将化合物13(1.5g,4.2mmol)、3,5-二叔丁基苯胺(432g,2.1mmol)、三(二亚苄基丙酮)二钯(311mg,0.34mmol)、2-二环己基膦-2′,6′-二甲氧基-联苯(317mg,0.68mmol)、叔丁醇钠(979mg,10.2mmol)加入100mL的圆底烧瓶中,抽真空充氩气反复3次后加入甲苯(60mL)。110℃下反应12小时,冷却至室温后用乙酸乙酯和水萃取粗产品,收集有机层。有机层反复水洗3次,收集有机层,减压蒸馏除去有机溶剂。粗产品经柱层析分离提纯,得到淡黄色固体产品1.4g,即化合物14,产率77.9%。1H NMR(400MHz,Chloroform-d)δ8.47(d,J=7.8Hz,2H),7.94(t,J=2.0Hz,2H),7.84(dt,J=7.8,1.2Hz,2H),7.69–7.64(m,4H),7.6–7.58(m,4H),7.56–7.53(m,4H),7.47(tt,J=6.9,1.5Hz,6H),7.41(t,J=7.9Hz,2H),7.33(ddd,J=8.0,6.4,1.7Hz,2H),7.19(ddd,J=8.0,2.3,1.0Hz,2H),7.15–7.12(m,3H),1.28(s,18H).
(6)将化合物14(1g,1.4mmol),氯亚铂酸钾(664mg,1.6mmol)和醋酸(40mL)加入至100mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应24小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到红色固体840mg,即圆偏振发光配合物材料1-12,产率68%。1H NMR(400MHz,Chloroform-d)δ8.03(d,J=8.8Hz,2H),7.84(d,J=7.9Hz,2H),7.74(d,J=8.6Hz,2H),7.61(t,J=7.8Hz,4H),7.55(t,J=1.8Hz,1H),7.51–7.46(m,2H),7.43(d,J=7.4Hz,2H),7.37–7.32(m,4H),7.30(d,J=1.8Hz,2H),7.09(dd,J=8.4,7.4Hz,2H),7.03(ddd,J=8.4,7.1,1.3Hz,2H),6.86(d,J=8.3Hz,2H),6.36–6.29(m,4H),1.38(s,18H).
实施例4
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)将化合物15(2.5g,12mmol)、化合物16(2.4g,12mmol)和四三苯基膦钯(300mg,0.26mmol)加入500mL的圆底两口瓶中,抽真空充氩气反复三次,再依次注入甲苯(72mL)、乙醇(24mL)和2M的碳酸钾水溶液(24mL)。85℃下反应12小时。冷却,反应液用二氯甲烷和水萃取,收集下层,减压蒸馏除去溶剂。粗产品经柱层析分离提纯,得到白色粉末产品2.0g,即化合物17,产率84%。1HNMR(500MHz,Chloroform-d)δ8.36(t,J=1.9Hz,1H),8.25(d,J=8.6Hz,1H),8.17(d,J=8.5Hz,1H),8.08(dt,J=7.7,1.3Hz,1H),7.85(d,J=3.3Hz,1H),7.84(d,J=1.6Hz,1H),7.75(ddd,J=8.4,6.8,1.5Hz,1H),7.59(ddd,J=7.9,2.1,1.0Hz,1H),7.55(ddd,J=8.1,6.9,1.2Hz,1H),7.40(t,J=7.9Hz,1H).
(2)将化合物17(1.5g,5.3mmol)、3,5-二叔丁基苯胺(1.1g,5.3mmol)、醋酸钯(120mg,0.53mmol)、四氟硼酸三叔丁基膦(307.4mg,1.0mmol)、叔丁醇钾(1.5g,16mmol)加入100mL的圆底烧瓶中,抽真空充氩气反复3次后加入甲苯(60mL)。110℃下反应12小时,冷却至室温后用乙酸乙酯和水萃取粗产品,收集有机层。有机层反复水洗3次,收集有机层,减压蒸馏除去有机溶剂。粗产品经柱层析分离提纯,得到黄褐色固体产品2.0g,即化合物18,产率92%。1H NMR(600MHz,Chloroform-d)δ8.20(d,J=8.6Hz,1H),8.14(d,J=8.5Hz,1H),7.98(s,1H),7.84(dd,J=19.5,8.3Hz,2H),7.73–7.69(m,1H),7.63(d,J=7.3Hz,1H),7.52(t,J=7.4Hz,1H),7.40(t,J=7.8Hz,1H),7.14(dd,J=8.0,2.5Hz,1H),7.07(s,3H),5.90(s,1H),1.35(s,18H).
(3)将化合物19(1.2g,3.4mmol)、化合物18(1.4g,3.4mmol)、三(二亚苄基丙酮)二钯(311mg,0.34mmol)、2-二环己基磷-2’,6’-二异丙氧基-1,1’-联苯(317mg,0.68mmol)、叔丁醇钠(979mg,10.2mmol)加入100mL的圆底烧瓶中,抽真空充氩气反复3次后加入甲苯(60mL)。110℃下反应12小时,冷却至室温后用乙酸乙酯和水萃取粗产品,收集有机层。有机层反复水洗3次,收集有机层,减压蒸馏除去有机溶剂。粗产品经柱层析分离提纯,得到淡黄色固体产品1.9g,即化合物20,产率77.7%。1H NMR(400MHz,Chloroform-d)δ8.47(d,J=7.9Hz,1H),8.16(d,J=8.7Hz,1H),7.97(t,J=2.0Hz,1H),7.91(t,J=2.0Hz,1H),7.86(d,J=7.8Hz,1H),7.82(d,J=8.4Hz,1H),7.79(d,J=8.4Hz,1H),7.76(d,J=8.7Hz,1H),7.71(d,J=5.7Hz,1H),7.68(s,1H),7.65(s,1H),7.63(s,1H),7.61(s,1H),7.59(s,1H),7.56(d,J=1.5Hz,1H),7.55–7.53(m,1H),7.50–7.49(m,1H),7.47(d,J=4.3Hz,2H),7.41(t,J=7.9Hz,3H),7.33(ddd,J=8.0,6.6,1.4Hz,1H),7.25–7.23(m,1H),7.21–7.17(m,1H),7.14–7.11(m,4H),1.27(s,
(4)将化合物20(1.4g,1.6mmol),氯亚铂酸钾(664mg,1.6mmol)和醋酸(40mL)加入至100mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应24小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到红色固体729mg,即圆偏振发光配合物材料1-13,产率39%。1H NMR(500MHz,Methylene Chloride-d2)δ8.35(d,J=8.7Hz,1H),8.23(d,J=8.7Hz,1H),8.12(d,J=8.8Hz,1H),8.02(dd,J=8.8,6.9Hz,2H),7.95(d,J=8.0Hz,1H),7.72(t,J=7.1Hz,2H),7.68–7.57(m,6H),7.47(d,J=7.4Hz,1H),7.26–7.14(m,4H),7.11–7.04(m,3H),6.77(ddd,J=8.5,6.9,1.5Hz,1H),6.34(ddd,J=25.4,17.8,8.2Hz,3H),1.39(s,18H).
实施例5
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)将化合物21(1.2g,5.3mmol)、3,5-二叔丁基苯胺(1.1g,5.3mmol)、醋酸钯(120mg,0.53mmol)、四氟硼酸三叔丁基膦(307.4mg,1.0mmol)、叔丁醇钾(1.5g,16mmol)加入100mL的圆底烧瓶中,抽真空充氩气反复3次后加入甲苯(60mL)。110℃下反应12小时,冷却至室温后用乙酸乙酯和水萃取粗产品,收集有机层。有机层反复水洗3次,收集有机层,减压蒸馏除去有机溶剂。粗产品经柱层析分离提纯,得到黄褐色固体产品1.8g,即化合物22,产率90%。1H NMR(500MHz,Chloroform-d)δ8.66(d,J=4.5Hz,1H),7.76–7.67(m,3H),7.48(d,J=7.7Hz,1H),7.35(t,J=7.8Hz,1H),7.21(t,J=6.0Hz,1H),7.13–7.10(m,1H),7.04(dd,J=15.1,1.7Hz,4H),1.33(s,18H).
(2)将化合物19(1.2g,3.4mmol)、化合物22(1.2g,3.4mmol)、三(二亚苄基丙酮)二钯(311mg,0.34mmol)、2-二环己基磷-2’,6’-二异丙氧基-1,1’-联苯(317mg,0.68mmol)、叔丁醇钠(979mg,10.2mmol)加入100mL的圆底烧瓶中,抽真空充氩气反复3次后加入甲苯(60mL)。110℃下反应12小时,冷却至室温后用乙酸乙酯和水萃取粗产品,收集有机层。有机层反复水洗3次,收集有机层,减压蒸馏除去有机溶剂。粗产品经柱层析分离提纯,得到淡黄色固体产品1.6g,即化合物23,产率72%。1H NMR(500MHz,Chloroform-d)δ8.67–8.64(m,1H),7.93–7.89(m,1H),7.86(dd,J=8.5,1.5Hz,2H),7.72–7.67(m,3H),7.66–7.62(m,4H),7.58(dd,J=8.4,1.5Hz,2H),7.52–7.47(m,3H),7.42(t,J=7.8Hz,1H),7.40–7.35(m,2H),7.24–7.17(m,3H),7.13(t,J=1.7Hz,1H),7.11(d,J=1.7Hz,2H),1.28(s,18H).
(3)将化合物23(1.0g,1.5mmol),氯亚铂酸钾(830mg,2mmol)和醋酸(40mL)加入至100mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应24小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到红色固体600mg,即圆偏振发光配合物材料1-14,产率46%。1H NMR(600MHz,Methylene Chloride-d2)δ8.66(d,J=8.1Hz,1H),8.45(d,J=5.1Hz,1H),7.99(d,J=8.7Hz,1H),7.89(dd,J=16.4,8.3Hz,2H),7.74–7.62(m,4H),7.60–7.53(m,2H),7.47–7.40(m,2H),7.37(d,J=7.3Hz,1H),7.31(d,J=7.3Hz,1H),7.19(d,J=1.8Hz,2H),7.04(t,J=7.9Hz,1H),6.98(t,J=7.9Hz,1H),6.94(ddd,J=7.9,6.3,1.5Hz,1H),6.72(t,J=6.5Hz,1H),6.29(dd,J=35.0,8.3Hz,3H),1.55(s,18H)
实施例6
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)将化合物24(2.5g,12mmol)、化合物16(2.4g,12mmol)和四三苯基膦钯(300mg,0.26mmol)加入500mL的圆底两口瓶中,抽真空充氩气反复三次,再依次注入甲苯(72mL)、乙醇(24mL)和2M的碳酸钾水溶液(24mL)。85℃下反应12小时。冷却,反应液用二氯甲烷和水萃取,收集下层,减压蒸馏除去溶剂。粗产品经柱层析分离提纯,得到白色粉末产品2.5g,即化合物25,产率74%。1HNMR(600MHz,Chloroform-d)δ9.33(s,1H),8.31(t,J=1.8Hz,1H),8.08–8.03(m,2H),8.03–7.99(m,1H),7.91–7.87(m,1H),7.72(ddd,J=8.2,6.8,1.3Hz,1H),7.62(ddd,J=8.1,6.8,1.2Hz,1H),7.54(ddd,J=8.0,2.0,1.0Hz,1H),7.38(t,J=7.9Hz,1H).
(2)将化合物25(1.5g,5.3mmol)、3,5-二叔丁基苯胺(1.1g,5.3mmol)、醋酸钯(120mg,0.53mmol)、四氟硼酸三叔丁基膦(307.4mg,1.0mmol)、叔丁醇钾(1.5g,16mmol)加入100mL的圆底烧瓶中,抽真空充氩气反复3次后加入甲苯(60mL)。110℃下反应12小时,冷却至室温后用乙酸乙酯和水萃取粗产品,收集有机层。有机层反复水洗3次,收集有机层,减压蒸馏除去有机溶剂。粗产品经柱层析分离提纯,得到黄褐色固体产品1.8g,即化合物26,产率83%。1H NMR(500MHz,Chloroform-d)δ9.31(s,1H),8.05(s,1H),7.99(d,J=8.1Hz,1H),7.90(d,J=2.2Hz,1H),7.83(d,J=8.1Hz,1H),7.71–7.67(m,1H),7.66–7.63(m,1H),7.58(ddd,J=8.0,6.8,1.1Hz,1H),7.39(t,J=7.8Hz,1H),7.11(dd,J=7.9,2.1Hz,1H),7.06(d,J=1.3Hz,3H),5.94–5.82(m,1H),1.35(d,J=1.1Hz,18H).
(3)将化合物19(1g,2.8mmol)、化合物26(1.2g,2.8mmol)、三(二亚苄基丙酮)二钯(3280mg)、2-二环己基磷-2’,6’-二异丙氧基-1,1’-联苯(317mg,0.68mmol)、叔丁醇钠(979mg,10.2mmol)加入100mL的圆底烧瓶中,抽真空充氩气反复3次后加入甲苯(60mL)。110℃下反应12小时,冷却至室温后用乙酸乙酯和水萃取粗产品,收集有机层。有机层反复水洗3次,收集有机层,减压蒸馏除去有机溶剂。粗产品经柱层析分离提纯,得到淡黄色固体产品1.7g,即化合物27,产率85%。1H NMR(500MHz,Chloroform-d)δ9.28(s,1H),8.46(d,J=7.8Hz,1H),7.98(t,J=2.0Hz,1H),7.95(d,J=8.1Hz,2H),7.91(t,J=2.0Hz,1H),7.85(dt,J=7.7,1.3Hz,1H),7.82–7.77(m,2H),7.69–7.65(m,2H),7.65–7.62(m,2H),7.60(d,J=7.6Hz,2H),7.56–7.53(m,3H),7.49–7.46(m,3H),7.40(dt,J=10.6,7.9Hz,2H),7.35–7.31(m,1H),7.22–7.17(m,2H),7.12(s,2H),1.27(s,18H).
(4)将化合物27(1.5g,2.1mmol),氯亚铂酸钾(1000mg,2.5mmol)和醋酸(40mL)加入至100mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应24小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到红色固体925mg,即圆偏振发光配合物材料1-15,产率48%。1H NMR(500MHz,Chloroform-d)δ9.27(s,1H),8.79(d,J=8.0Hz,1H),8.19(s,1H),8.04(d,J=8.7Hz,1H),7.95(d,J=8.6Hz,1H),7.84(d,J=8.2Hz,1H),7.73(d,J=7.1Hz,4H),7.67–7.63(m,1H),7.61(td,J=8.7,8.3,2.0Hz,1H),7.56(t,J=1.8Hz,1H),7.53(d,J=7.4Hz,1H),7.49(d,J=8.3Hz,1H),7.37(d,J=7.4Hz,1H),7.36–7.32(m,1H),7.30(d,J=1.8Hz,3H),7.17–7.11(m,1H),7.10–7.07(m,1H),7.05(d,J=7.9Hz,1H),6.73(t,J=7.5Hz,1H),6.40(d,J=8.3Hz,1H),6.37(d,J=8.3Hz,1H),1.40(s,18H).
实施例7
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)将化合物28(5g,18.3mmol)、3,5-二叔丁基苯胺(3.7g,18.3mmol)、醋酸钯(120mg,0.53mmol)、四氟硼酸三叔丁基膦(1g,3.7mmol)、叔丁醇钾(10g,91mmol)加入2500mL的圆底烧瓶中,抽真空充氩气反复3次后加入甲苯(100mL)。110℃下反应12小时,冷却至室温后用乙酸乙酯和水萃取粗产品,收集有机层。有机层反复水洗3次,收集有机层,减压蒸馏除去有机溶剂。粗产品经柱层析分离提纯,得到黄褐色固体产品6.2g,即化合物29,产率85%。1H NMR(500MHz,Chloroform-d)δ8.10(s,1H),7.88–7.83(m,1H),7.62–7.58(m,1H),7.40(t,J=8.0Hz,1H),7.35–7.28(m,2H),7.12(dd,J=4.6,2.0Hz,2H),7.07–7.03(m,3H),6.96(ddd,J=7.8,2.0,0.9Hz,1H),5.91(s,1H),1.33(s,18H).
(2)将化合物29(2g,5mmol)、化合物19(1.8g,5mmol)、醋酸钯(17mg,0.1mmol)、四氟硼酸三叔丁基膦(0.29g,1mmol)、叔丁醇钾(2.8g,25mmol)加入2500mL的圆底烧瓶中,抽真空充氩气反复3次后加入甲苯(100mL)。110℃下反应12小时,冷却至室温后用乙酸乙酯和水萃取粗产品,收集有机层。有机层反复水洗3次,收集有机层,减压蒸馏除去有机溶剂。粗产品经柱层析分离提纯,得到黄褐色固体产品2.6g,即化合物30,产率72%。1H NMR(600MHz,Chloroform-d)δ8.49(d,J=7.8Hz,1H),8.13(t,J=2.0Hz,1H),7.89–7.85(m,2H),7.79(d,J=8.6Hz,1H),7.74(d,J=8.6Hz,1H),7.68(dd,J=8.3,7.3Hz,2H),7.63–7.60(m,2H),7.58–7.51(m,4H),7.47(t,J=7.8Hz,1H),7.43(t,J=8.0Hz,1H),7.38(ddd,J=7.9,6.6,1.3Hz,1H),7.30–7.27(m,2H),7.26(dq,J=5.3,1.8,1.4Hz,2H),7.22–7.19(m,1H),7.18(d,J=1.8Hz,2H),7.14(ddd,J=8.2,7.2,1.1Hz,1H),7.10–7.06(m,1H),1.34(s,18H).
(3)将化合物30(2g,2.8mmol)加入至250mL双口烧瓶中,抽真空充氩气反复3次后加入四氢呋喃100mL,再注入碘甲烷(4g,28mmol)。70℃下反应48小时,冷却至室温后减压蒸馏除去溶剂和剩余的碘甲烷,得到黄色固体产品2.4g,即化合物31,产率90%。
(4)将化合物31(1g,1.2mmol),氯亚铂酸钾(581mg,1.4mmol)和醋酸(30mL)加入至100mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应24小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到红色固体454mg,即圆偏振发光配合物材料1-36,产率41%。[M]+:923.1.
实施例8
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)将化合物32(2.0g,7.8mmol),化合物33(1.1g,7.8mmol),四三苯基膦钯(180mg)和碳酸钾(4.3g)置于250mL双口圆底烧瓶中,再依次注入50mL甲苯,20mL乙醇和16mL水。搅拌加热至85℃反应24小时。冷却,反应液用二氯甲烷和水萃取,收集下层,减压蒸馏除去溶剂。粗产品经柱层析分离提纯,得到白色粉末产品1.1g,即化合物34,产率52%。1HNMR(500MHz,Chloroform-d)δ9.35(s,1H),8.70(d,J=8.6Hz,1H),8.27–8.15(m,2H),7.97(d,J=8.3Hz,1H),7.94–7.88(m,1H),7.84–7.66(m,4H),7.52–7.41(m,2H).
(2)将化合物34(1g,3.7mmol),化合物35(1.1g,3.7mmol)和碳酸钾(2.1g,14.8mmol)加入到100mL的圆底烧瓶中,抽真空充氩气反复3次后注入60mL N-甲基吡咯烷酮。搅拌加热至180℃反应72小时。冷却,反应液用二氯甲烷和水萃取,收集下层,减压蒸馏除去溶剂。粗产品经柱层析分离提纯,得到白色粉末产品0.73g,即化合物36产率60%。1HNMR(500MHz,Chloroform-d)δ8.58(d,J=8.6Hz,2H),8.25–8.12(m,4H),8.03(d,J=8.3Hz,2H),7.94–7.88(m,2H),7.84(m,6H),7.52–7.41(m,2H)7.35(m,6H).
(3)将化合物36(500mg,0.95mmol),氯亚铂酸钾(498mg,1.2mmol)和醋酸(30mL)加入至100mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应24小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到产品327mg,即圆偏振发光配合物材料2-1,产率48%。1H NMR(500MHz,Chloroform-d)δ8.35(d,J=8.6Hz,2H),8.20–8.12(m,4H),8.13(d,J=8.3Hz,2H),7.94–7.86(m,2H),7.66(m,6H),7.52–7.41(m,2H)7.33(m,4H).
实施例9
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)将化合物37(2g,5.8mmol),Pd(dppf)2Cl2(85mg)和醋酸钾(2.8g,29mmol)加入至250mL的两口圆底烧瓶中抽真空充氩气反复3次后注入100mL 1,4-二氧六环。搅拌加热至135℃反应48小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到产品1.8g,即化合物38,产率72%。1H NMR(500MHz,Chloroform-d)δ7.35(d,J=4.8,2H),7.17(m,4H),7.52–7.41(m,2H)7.08(m,2H),6.68(d,J=6.8,2H),1.35(s,24H)
(2)将化合物38(1.5g,3.4mmol),化合物39(2.2g,8.5mmol),四三苯基膦钯(180mg)和碳酸钾(3.7g)置于250mL双口圆底烧瓶中,再依次注入50mL甲苯,20mL乙醇和16mL水。搅拌加热至85℃反应24小时。冷却,反应液用二氯甲烷和水萃取,收集下层,减压蒸馏除去溶剂。粗产品经柱层析分离提纯,得到白色粉末产品899mg,即化合物40,产率49%。1H NMR(500MHz,Chloroform-d)δ8.66(d,J=8.6Hz,2H),8.38–8.25(m,4H),8.12(d,J=8.3Hz,2H),7.80–7.35(m,2H),7.84(m,6H),7.24–7.10(m,2H)6.88(m,6H).
(3)将化合物40(500mg,0.91mmol),氯亚铂酸钾(498mg,1.2mmol)和醋酸(30mL)加入至100mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应24小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到产品327mg,即圆偏振发光配合物材料3-1,产率45%。1H NMR(500MHz,Chloroform-d)δ8.42(d,J=8.6Hz,2H),8.28–8.18(m,4H),8.15(d,J=8.3Hz,2H),7.88–7.72(m,2H),7.66(m,6H),7.52–7.32(m,2H)7.13(m,4H).
实施例10
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)在250mL三口烧瓶中,加入化合物41(2g,6mmol)镁屑(10g,416mmol),碘单质(5.3g,416mmol)和100mL HPLC级别四氢呋喃溶剂。于50℃下搅拌反应4小时,备用。
-78℃下,在500mL双口烧瓶中加入化合物42(786mg,3mmol)和150mL HPLC级别四氢呋喃溶剂,抽真空充氩气反复3次。缓慢向反应容器内滴加2.5M的正丁基锂溶液(5mL)。反应1小时后,逐滴加入前述反应液。升温至室温后继续反应过夜。反应结束后注入10mL水淬灭。反应液用二氯甲烷和水萃取,收集下层,减压蒸馏除去溶剂。粗产品经柱层析分离提纯,得到产品212mg,即化合物43,产率10%。1H NMR(400MHz,Chloroform-d)δ9.32–9.27(m,2H),8.22–8.10(m,4H),8.05(dt,J=7.7,1.3Hz,2H),7.95(s,2H),7.89–7.83(m,2H),7.66(t,J=8.8Hz,2H),7.60–7.50(m,6H),7.27(t,J=7.9Hz,2H),7.15–6.98(m,2H),6.88(dd,J=15.6,1.8Hz,3H),7.52(s,1H),1.30(s,18H).
(2)将化合物43(150mg,0.21mmol),氯亚铂酸钾(124mg,0.3mmol)和醋酸(10mL)加入至25mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应72小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到产品56mg,即圆偏振发光配合物材料4-1,产率30%。1H NMR(400MHz,Chloroform-d)δ9.33(d,J=4.8Hz,2H),8.15(d,J=4.8Hz,2H),8.04(d,J=8.3Hz,2H),7.62(t,J=2.0Hz,1H),7.54(d,J=7.4Hz,2H),7.42–7.31(m,4H),7.24(s,2H),7.19(dd,J=8.3,7.4Hz,2H),7.12(d,J=8.7Hz,2H),7.05(ddd,J=8.0,6.9,1.2Hz,2H),6.54(ddd,J=8.3,7.0,1.3Hz,2H),6.42(d,J=8.3Hz,2H),1.40(s,18H).
实施例11
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)将化合物44(2g,4mmol),Pd(dppf)2Cl2(85mg)和醋酸钾(1.6g,16mmol)加入至250mL的两口圆底烧瓶中抽真空充氩气反复3次后注入100mL 1,4-二氧六环。搅拌加热至135℃反应48小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到产品1.9g,即化合物45,产率81%。1HNMR(500MHz,Chloroform-d)δ7.66(s,2H),7.38–7.25(m,8H),7.12(d,J=8.3Hz,2H),7.80–7.35(m,2H),7.84(m,2H),7.24–7.10(m,2H),1.35(s,24H).
(2)将化合物45(1.5g,2.6mmol),化合物46(1.2g,,5.7mmol),四三苯基膦钯(80mg)和碳酸钾(2.7g)置于250mL双口圆底烧瓶中,再依次注入50mL甲苯,15mL乙醇和10mL水。搅拌加热至85℃反应24小时。冷却,反应液用二氯甲烷和水萃取,收集下层,减压蒸馏除去溶剂。粗产品经柱层析分离提纯,得到白色粉末产品771mg,即化合物47,产率43%。1HNMR(500MHz,Chloroform-d)δ9.68(d,J=8.1Hz,2H),8.44(d,J=8.5Hz,2H),8.31(d,J=8.4Hz,2H),7.78(t,J=1.8Hz,2H),7.76–7.61(m,2H),7.49–7.43(m,2H),7.33(d,J=8.7Hz,2H),7.29-7.20(m,8H),7.17–7.06(m,8H),6.64(ddd,J=8.2,6.8,1.3Hz,2H),6.35(dd,J=8.3,0.9Hz,2H).
(3)将化合物47(500mg,0.721mmol),氯亚铂酸钾(361m,87mmol)和醋酸(35mL)加入至100mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应72小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到产品248mg,即圆偏振发光配合物材料5-1,产率39%。1H NMR(500MHz,Chloroform-d)δ9.48(d,J=8.1Hz,2H),8.42(d,J=8.5Hz,2H),7.76(t,J=1.8Hz,2H),7.70–7.61(m,2H),7.52–7.43(m,2H),7.31(d,J=8.7Hz,2H),7.29-7.20(m,8H),7.15–7.06(m,8H),6.62(ddd,J=8.2,6.8,1.3Hz,2H),6.38(dd,J=8.3,0.9Hz,2H).
实施例12
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)将实施例1中获得的化合物4(1g,1.4mmol),醋酸钯(232mg,1.4mmol)和醋酸(40mL)加入至100mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应24小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到红色固体114mg,即圆偏振发光配合物材料11-1,产率10%。1H NMR(500MHz,Acetone-d6)δ9.48(d,J=8.1Hz,2H),8.40(d,J=8.5Hz,2H),8.29(d,J=8.4Hz,2H),7.73(t,J=1.8Hz,1H),7.66–7.61(m,2H),7.49–7.43(m,2H),7.35(d,J=8.7Hz,2H),7.32–7.26(m,4H),7.17–7.06(m,4H),6.64(ddd,J=8.2,6.8,1.3Hz,2H),6.35(dd,J=8.3,0.9Hz,2H)
实施例13
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)将化合物48(2g,7mmol)、3,5-二叔丁基苯胺(717mg,3.5mmol)、醋酸钯(23mg,0.1mmol)、三叔丁基磷四氟硼酸盐(290mg,1mmol)、叔丁醇钾(4g,35mmol)加入250mL的圆底烧瓶中,抽真空充氩气反复3次后加入甲苯(100mL)。110℃下反应12小时,冷却至室温后用乙酸乙酯和水萃取粗产品,收集有机层。有机层反复水洗3次,收集有机层,减压蒸馏除去有机溶剂。粗产品经柱层析分离提纯,得到黄褐色固体产品1.7g,即为化合物49,产率84%。1HNMR(600MHz,Chloroform-d)δ8.14(dd,J=20.9,8.5Hz,4H),7.96(t,J=2.0Hz,2H),7.84–7.77(m,4H),7.75(d,J=8.6Hz,2H),7.69(t,J=7.4Hz,2H),7.50(t,J=7.5Hz,2H),7.41(t,J=7.9Hz,2H),7.23(ddd,J=8.1,2.4,1.0Hz,2H),7.13(t,J=1.7Hz,1H),7.10(d,J=1.7Hz,2H),1.26(s,18H).
(2)将化合物49(1g,1.6mmol),醋酸钯(366mg,1.6mmol)和醋酸(40mL)加入至100mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应24小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到红色固体114mg,即圆偏振发光配合物材料11-7,产率10%。1H NMR(500MHz,Chloroform-d)δ8.30(d,J=8.6Hz,2H),8.17(d,J=8.7Hz,2H),7.77(dd,J=8.1,1.4Hz,2H),7.67(d,J=8.6Hz,2H),7.62–7.58(m,2H),7.53(t,J=1.8Hz,1H),7.30–7.26(m,2H),7.21(d,J=1.8Hz,2H),7.10(dd,J=8.3,7.4Hz,2H),6.85(ddd,J=8.5,6.9,1.4Hz,2H),6.40(dd,J=8.3,0.9Hz,2H),1.35(s,18H).
实施例14
本实施例提供一种圆偏振发光配合物材料的制备方法,制备流程如下:
(1)将实施例2中获得的化合物7(1g,1.4mmol),醋酸钯(232mg,1.4mmol)和醋酸(40mL)加入至100mL的两口圆底烧瓶中。用氩气鼓泡30分钟后于135℃下反应24小时。冷却至室温后过滤,收集固体。粗产品经柱层析过柱分离,得到红色固体230mg,即圆偏振发光配合物材料11-8,产率20%。1H NMR(500MHz,DMSO-d6)δ8.63(d,J=8.7Hz,2H),8.53(d,J=8.9Hz,2H),8.03(dd,J=8.1,1.4Hz,2H),7.74(d,J=1.7Hz,2H),7.59–7.50(m,3H),7.41(ddd,J=8.1,6.9,1.1Hz,2H),7.09(d,J=1.8Hz,2H),6.96(ddd,J=8.4,6.8,1.5Hz,2H),6.38(d,J=1.7Hz,2H),1.35(s,18H),1.17(s,18H).
试验例1
测定实施例1、3、4和12手性制备柱的HPLC分离效果。测试条件:Column size:0.46cm I.D.×25cm L;Injection:0.5ul;Mobile phase:DCM=100%;Flow rate:1.0ml/min;Wave length:UV 254nm;Temperature:35℃;HPLC equipment:Shimadzu LC-20AT CP-HPLC-09。结果如表1和图1-4:
表1各实施例手性分离数据
实施例 | 峰1保留时间(min) | 峰2保留时间(min) |
1 | 4.54 | 5.03 |
3 | 4.58 | 5.11 |
4 | 4.69 | 6.52 |
12 | 5.75 | 7.80 |
由表1和图1-4数据可知,各实施例均有较好的分离度,可大量手性制备。
试验例2
测定各实施例在二氯甲烷溶液中紫外吸收光谱、光致发光光谱以及实施例圆偏振光致发光谱图,结果如表2所示:
表2各实施例物理性质数据
实施例 | 吸收峰波长[nm] | 发射峰波长[nm] | 分解温度[℃] |
1 | 400/550 | 690 | 358 |
2 | 380/450/600 | 735 | 356 |
3 | 364/433/578 | 664 | 402 |
4 | 368/430/588 | 709 | 393 |
5 | 348/437/556 | 645 | 415 |
6 | 345/434/555 | 641 | 399 |
7 | 339/431/540 | 635 | 420 |
8 | 310/450 | 525 | 398 |
9 | 325/455 | 545 | 400 |
10 | 330/448 | 585 | 399 |
11 | 332/452 | 568 | 420 |
12 | 292/345/501 | 602 | 341 |
13 | 277/358/521 | 635 | 337 |
14 | 279/365/540 | 640 | 330 |
由表2的数据可见,各实施例配合物适合做红光至近红外掺杂剂,在5wt%时的分解温度均高于330摄氏度,表明实施例配合物具有良好的热稳定性。
试验例3
对实施例1进行放大量手性制备,制备前后效果如图5-图7所示。结果表明,在数百毫克级别下,实施例1样品能有效进行手性拆分,获得两组ee值均在97%左右的组分,为对映异构体。
表3.实施例1手性制备后ee值数据
样品名称 | 样品状态 | ee值 | 产品质量/g |
制备前 | 黑色粉末 | -- | 0.2801 |
Peak 1 | 棕色固体 | >96.5% | 0.1157 |
Peak 2 | 棕色固体 | >97.5% | 0.1121 |
试验例4
对实施例1进行圆偏振吸收和发射测试,分别在二氯甲烷溶液和薄膜状态下测试,激发波长为450nm。结果如图8-图12所示,可以看到,实施例1在二氯甲烷和薄膜状态下均有较强的圆偏振吸收和发射信号,其g因子可达2×10-3,说明本发明实现了圆偏振发光的目的,可以实现较好的CPL信号效果。
试验例5
以测定基于实施例1、2、3、4、5、6、7、12、13和14的电致发光器件的电致发光性能,说明本发明配合物在电致发光器件中的应用。电致发光器件结构为:ITO/HATCN(5nm)/TPD15(30nm)/TCTA(15nm)/DMIC-CZ+DMIC-TRZ+本发明手性配合物(3种化合物比例为100:100:6)(50nm)/ANT-BIZ(30nm)/Liq(2nm)/Al(100nm),结构中除本发明手性配合物之外的结构式如下,结果如下表4所示:
表4各实施例器件表征结果
注:T90为器件运行至亮度为初始亮度值的90%所消耗的时间。
结果表明,本发明实施例电致发光器件有较好的电致红光和电致近红外发光性能,且器件运行稳定性较好。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (6)
1.一种圆偏振发光配合物材料,其特征在于,所述圆偏振发光配合物材料包括式Ⅰ表示的化合物:
其中,M为铂或钯;
A、B、C和D各自独立的选自氮或卡宾碳原子;
环L1、环L2、环L3以及环L4各自独立选自多元芳环、芳香杂环、具有一个或多个取代基的芳环或芳香杂环,所述取代基各自独立选自H、D、F、Cl、Br、I、-CN、-NO2、-CF3、-OH、-SH、-NH、-NH2、C1-C30的直连烷烃、C3-C30的支链烷烃、C3-C30的环烷基、C1-C30的烷氧基/烷巯基、C6-C60的芳基/杂芳基/醚基/芳杂醚基;其中,杂芳基的杂原子可以独立选自Si、Ge、N、P、O、S、Se;
-------表示相邻的环L1、环L2、环L3以及环L4相互连接或独立存在,所述连接为通过化学键键连或稠成环。
6.权利要求1-5任一项所述圆偏振发光配合物材料的应用,其特征在于,应用于手性药物、手性农药、手性液晶材料、手性导电聚合物材料、手性介孔材料、手性纳米材料和手性电致发光材料。
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