CN111303015B - 一种具有aie效应的有机小分子的制备及应用 - Google Patents

一种具有aie效应的有机小分子的制备及应用 Download PDF

Info

Publication number
CN111303015B
CN111303015B CN202010094654.0A CN202010094654A CN111303015B CN 111303015 B CN111303015 B CN 111303015B CN 202010094654 A CN202010094654 A CN 202010094654A CN 111303015 B CN111303015 B CN 111303015B
Authority
CN
China
Prior art keywords
compound
reaction
preparation
aie
molar ratio
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
Application number
CN202010094654.0A
Other languages
English (en)
Other versions
CN111303015A (zh
Inventor
肖唐鑫
鲍成
吴可慧
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changzhou University
Original Assignee
Changzhou University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Changzhou University filed Critical Changzhou University
Priority to CN202010094654.0A priority Critical patent/CN111303015B/zh
Publication of CN111303015A publication Critical patent/CN111303015A/zh
Application granted granted Critical
Publication of CN111303015B publication Critical patent/CN111303015B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/127—Preparation from compounds containing pyridine rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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
    • 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • 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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1416—Condensed systems
    • 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
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
    • 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
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Pyridine Compounds (AREA)

Abstract

一种基于芴基的二吡啶化合物的制备方法。所述化合物为基于9‑芴酮与4‑吡啶硼酸为起始原料所合成的化合物。基于吡啶对钯离子络合的原理，该化合物对钯离子有聚集诱导发光(AIE)效应。本发明的有益效果如下：该分子的结构简单，合成方便，是一种很好的自发光AIE配体，在金属配位材料里面有非常大的潜在应用；该方法合成的化合物在荧光凝胶领域有广阔的应用前景。

Description

一种具有AIE效应的有机小分子的制备及应用
技术领域
本发明属于超分子材料的合成领域，具体涉及一种可逆凝胶-溶胶聚合物发光材料的制备。
背景技术
传统的发光材料是在溶液中发光，而在聚集状态下不发光的，这种现象叫做荧光淬灭(aggregation-caused quenching,ACQ)，这是由于分子间相互作用使非辐射跃迁增加，导致荧光减弱。2001年唐本忠教授首次发现了某些物质在溶液中不发光，而在聚集状态下发光的现象，将这一现象命名为聚集诱导发光效应(aggregation-induced emission,AIE)，主要原因是由于分子内的运动受限，减少了非辐射能的衰减。
本发明中，我们创新地合成了一种芴取代的二吡啶化合物，该化合物仍具有AIE效应，并且在金属配体配位驱动下，可以形成一种具有AIE效应的金属有机凝胶。由于该化合物具有热和稀释诱导的可逆凝胶-溶胶转化，表明其作为发光材料有巨大的潜在应用价值。
发明内容
本发明的目的旨在合成一种芴的二吡啶化合物，通过金属配体Pd(OAc)2配位驱动的自组装，形成一种具有AIE效应的金属配位有机凝胶。
所述化合物为一种芴的二吡啶化合物(记为化合物B)，具有如下化学结构：
Figure BDA0002384950580000011
其合成路线如下：
Figure BDA0002384950580000012
所述化合物B的合成方法，包括以下步骤：
步骤1，化合物A的合成：于反应容器中加入9-芴酮，在N2氛围下，加入有机溶剂二氯甲烷搅拌至溶解，加入CBr4和PPh3，设置反应温度为40℃，搅拌24h，反应完毕，停止搅拌。冷却至室温后向反应液中加入石油醚，硅藻土抽滤三次，将滤液旋干，然后柱层析进一步纯化，得到黄色固体粉末，即为化合物A。
步骤2，化合物B的合成：在反应容器中加入化合物A，在氮气氛围下，冰盐浴条件下Dioxane/H2O(4:1)溶液，搅拌至完全溶解，加入Na2CO3，Pd(OAc)2，PPh3，4-吡啶硼酸，逐渐升温至回流，搅拌12h。搅拌加热回流。反应完全后停止反应，冷却后将反应液倒入蒸馏水中，并用CH2Cl2萃取，合并有机相，向有机相加入饱和NaCl溶液进行淬灭，EA萃取，无水MgSO4干燥。过滤、旋干后过柱层析，得到白色固体，即为目标产物化合物B。所述化合物B粉末在紫外光激发下产生青蓝色荧光，证明其虽然有吡啶基取代，仍然具有AIE效应。
进一步地，步骤1中，所述氮气氛围是抽真空后充氮气可连续抽真空后充氮气循环3～5次所述对9-芴酮、CBr4和PPh3三者的摩尔比为1:2:4；抽滤次数为2～3次；所述柱层析洗脱剂为石油醚。
进一步地，步骤2中，所述化合物A和4-吡啶硼酸的摩尔比为1:2.5；所述氮气氛围是抽真空后充氮气可连续抽真空后充氮气循环3～5次；所述洗涤次数为2～3次；所述柱层析洗脱剂为EA:PE＝1:1。
所述化合物B与Pd(OAc)2络合，形成结构规整的链状化合物，其结构如下：
Figure BDA0002384950580000021
该链状超分子聚合物由于自身骨架的刚性，在一定浓度溶液中进一步自组装成有机凝胶。该AIE金属有机凝胶在加热和冷却时表现出可逆的凝胶-溶胶相变，而且通过稀释和浓缩也可以实现可逆的凝胶-溶胶相变，这种可逆循环可以重复多次，表明该凝胶可以重复利用，具有可回收性。
通过以上步骤合成，本发明的有益效果如下：
(1))本发明合成了一种全新的双吡啶配体分子B，本身具有AIE效应，在低温或高浓度下，吡啶环旋转受限，产生荧光；随着温度逐渐升高或浓度逐渐降低，荧光也随之减弱，这种具有配位点的AIE配体分子，可以运用于多种金属配位材料中；
(2)本发明提出的具有聚集诱导发光(AIE)效应的金属有机凝胶由基于芴的二吡啶化合物，通过金属配位驱动的自组装形成的，制作工艺简单，产率高，还具有荧光效果；
(3)该金属有机凝胶由单体化合物B和Pd(OAc)2络合而成，络合之后吡啶环旋转受限，产生荧光，具有聚集诱导发光现象(AIE)。而PPh3中的磷离子与钯离子具有竞争性，往其中加入三苯基膦后，该凝胶的链状结构遭到破坏，不管是在高浓度还是低温下，都不会显出荧光。
具体实施方式
现在结合具体实施例对本发明做进一步说明，以下实施例旨在说明而不是对本发明的进一步限定。
实施例1
化合物A的制备：于500mL三口烧瓶中加入3.60g的9-芴酮，在氮气氛围下，加入100mL的二氯甲烷搅拌至完全溶解，加入13.3g CBr4，然后缓慢加入21.0g的PPh3，升温至40℃下搅拌回流24h。反应完毕，停止加热搅拌，冷却至室温，向反应液中加入大量的石油醚，有固体和油状物生成，然后用硅藻土抽滤，将滤液旋干，粗产品进一步提纯，柱层析的过柱子得黄色固体5.21g，产率为78％。
化合物B的制备：于250mL三口烧瓶中加入1.0g的化合物A，在氮气氛围下，冰盐浴条件下，加入50mL的Dioxane/H2O(4:1)溶液，搅拌至完全溶解。加入800mg的Na2CO3，80mg的Pd(OAc)2，393mg的PPh3，900mg的4-吡啶硼酸，逐渐升温至回流，搅拌12h。TLC监测反应完全后，停止反应。向反应液中加入饱和NaCl溶液淬灭反应，用EA萃取，合并有机相。饱和NaCl溶液洗涤，无水MgSO4干燥，过滤，旋蒸，柱层析(EA:PE＝1:1)得到白色固体粉末800mg，产率为82％。
金属有机凝胶材料的制备：将化合物B与Pd(OAc)2按1:1的摩尔比加入CHCl3溶液中，室温放置24h，365nm下观察到溶液有荧光，而且随着化合物B与Pd(OAc)2两者络合浓度的不断升高，荧光强度不断增强。
虽然在上述实施例中已经具体描述了本发明的实施方案，但本领域的技术人员应当明白，这些只是为了举例说明，在不偏离本发明实质和范围的情况下，对本发明技术方案及其实施方式进行的多种变换或改进，均落入本发明的范围内。本发明的保护范围可以由权利要求书限定。

Claims (1)

1.一种金属有机凝胶材料的制备方法，其特征在于，包括以下步骤：
步骤一，N2氛围下，于反应容器中加入化合物9-芴酮、四溴化碳、三苯基膦，摩尔比为1:2:4，所述反应溶剂为二氯甲烷，加热至40℃，反应24h，反应完全后停止反应，向反应液中加入大量石油醚，并剧烈搅拌，用滤纸加硅藻土抽滤三次，柱层析精致得纯化合物A；
Figure FDA0003958604740000011
步骤二，于反应容器中加入化合物A，在冰盐浴条件下，加入1,4-二氧六环/水(4:1)溶液，搅拌溶解；再加入化合物4-吡啶硼酸、醋酸钯、三苯基膦、碳酸钠，逐渐升温至回流，反应12h；所述反应化合物A、4-吡啶硼酸、醋酸钯、三苯基膦、碳酸钠的摩尔比为1:2.5:0.12:2.5:2.5；反应完全后，停止反应，待体系冷却至室温，加入饱和氯化钠溶液和乙酸乙酯淬灭反应，分液后，用乙酸乙酯萃取水相，合并有机相，干燥，旋蒸，经柱层析得目标产物B；
Figure FDA0003958604740000012
金属有机凝胶材料的制备：将化合物B与Pd(OAc)2按1:1的摩尔比加入CHCl3溶液中，室温放置24h，365nm下观察到溶液有荧光，而且随着化合物B与Pd(OAc)2两者络合浓度的不断升高，荧光强度不断增强。
CN202010094654.0A 2020-02-16 2020-02-16 一种具有aie效应的有机小分子的制备及应用 Active CN111303015B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010094654.0A CN111303015B (zh) 2020-02-16 2020-02-16 一种具有aie效应的有机小分子的制备及应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010094654.0A CN111303015B (zh) 2020-02-16 2020-02-16 一种具有aie效应的有机小分子的制备及应用

Publications (2)

Publication Number Publication Date
CN111303015A CN111303015A (zh) 2020-06-19
CN111303015B true CN111303015B (zh) 2023-01-31

Family

ID=71158235

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010094654.0A Active CN111303015B (zh) 2020-02-16 2020-02-16 一种具有aie效应的有机小分子的制备及应用

Country Status (1)

Country Link
CN (1) CN111303015B (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115785471B (zh) * 2022-12-16 2023-08-08 华中科技大学 一种二氧化碳基超分子聚合物及其制备方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110615758A (zh) * 2019-10-15 2019-12-27 江南大学 具有聚集诱导发光效应的9-二(4-吡啶)乙烯-芴的制备方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110615758A (zh) * 2019-10-15 2019-12-27 江南大学 具有聚集诱导发光效应的9-二(4-吡啶)乙烯-芴的制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
AIE-ligand-based luminescent Cd(II)–organic framework as the first ‘‘turn-on’’ Fe3+ sensor in aqueous medium;Jinfang Zhang,等;《J. Mater. Chem.》;20191209;1427-1432，1428页左栏最后一段，1430页左栏第一段，scheme1和2，fig.2和3 *
Jinfang Zhang,等.AIE-ligand-based luminescent Cd(II)–organic framework as the first ‘‘turn-on’’ Fe3+ sensor in aqueous medium.《J. Mater. Chem.》.2019,1427-1432. *

Also Published As

Publication number Publication date
CN111303015A (zh) 2020-06-19

Similar Documents

Publication Publication Date Title
CN111187301B (zh) 一类聚集诱导发光铱配合物的制法及应用
CN111303049A (zh) 一种水分散性的荧光超分子聚合物纳米球的制备方法
CN108772027B (zh) 一种超分子有机凝胶及其金属凝胶的制备和应用
Bhattacharjee et al. Induction of photoluminescence and columnar mesomorphism in hemi-disc salphen type Schiff bases via nickel (II) coordination
CN111303015B (zh) 一种具有aie效应的有机小分子的制备及应用
Zhang et al. Synthesis and characterization of highly fluorescent europium functionalized β-diketonate complexes
Lin et al. Synthesis of alkynylated photo-luminescent Zn (II) and Mg (II) Schiff base complexes
Renouard et al. Functionalized tetradentate ligands for Ru-sensitized solar cells
CN110746423B (zh) 芳基咪唑并菲啰啉荧光染料的合成及对金属离子的识别
CN111793095A (zh) 一类环金属铂配合物的制法及应用
Zhang et al. Synthesis of carbazole derivatives with high quantum yield and high glass transition temperature
CN111233753A (zh) 一种aie金属有机凝胶的制备方法
CN113072592B (zh) 一种咔唑桥联双核金属铂配合物及其制备方法和应用
CN109384786B (zh) 基于咪唑的同分异构体发光分子及其制备方法与应用
CN108558595B (zh) 一种对苯撑乙烯桥联三聚茚衍生物及其制备方法
CN104628753A (zh) 一种meso位三苯胺类取代3,5位芳基修饰的氟化硼络合二吡咯甲川衍生物及其制备方法
CN109232169A (zh) 一种多芳基取代富瓦烯化合物及其合成方法
CN115785466B (zh) 一种具有绿色光氧化效应的超分子材料的制备方法及应用
CN116425764B (zh) 一种含三嗪和咔唑的热激活延迟荧光大环分子及其制备方法和应用
CN108424765B (zh) 一种黄色磷光Cu(I)配合物发光材料及其制备方法
CN115232161B (zh) 一种三聚茚基-bodipy-苝二酰亚胺三元体系分子及其制备方法
CN114907376B (zh) 一种基于双间苯-32-冠-10主体穴醚的分子机器及其制备方法
CN116144034B (zh) 具有近红外荧光的金属三角形超分子、制备方法及其应用
CN101481610B (zh) 一种以铱为内核的有机磷光材料及其制备方法
CN111732532B (zh) 一种合成具有缺电子基团的四芳基取代乙烯衍生物的方法

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