Induced Absolute Configuration of Achiral Tetradentate Ligands in Metal-Organic Frameworks for Circularly Polarized Luminescence

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外文摘要：The crystallization of chiral molecules is of great significance to understand the origin and evolution of hierarchical chirality and reveal the relationships between structural chirality and circularly polarized luminescence(CPL)activity.Here,we report two pairs of chiral metal-organic frameworks(MOFs)(DCF-17/LCF-17,DCF-18/LCF-18)by utilizing tetradentate ligands tetra(3-imidazoylphenyl)ethylene(TIPE)and 4,4'-[4',5'-bis[4-(4-pyridinyl)phenyl][1,1':2',1"-terphenyl]-4,4"-diyl]bis[pyridine](TPPP)as linkers.It can be observed that the spontaneous resolution of the achiral ligands is converted into the induced resolution,and the ligands form the absolute configu-ration by using enantiopure camphoric acid(cam)as chiral induced reagent(CIR).As a result,the racemate MOFs can be driven to generate absolute homochiral crystallization.Another two achiral MOFs[Cd(D-cam)(TPPP)0.5](AF-1,AF=achiral framework)and[Cd(L-cam)(TPPP)0.5](AF-2)were prepared.The position disorder of D/L-cam skeleton causes the generation of nonchiralization,fur-ther leading to disappearance of symmetry breaking of TPPP.For the perspective of structure,this is the first report which reveals the chiral transfer and nonchiralization between chiral induced agents and tetradentate ligands.Besides,DCF-17 and LCF-17 show CPL with luminescence dissymmetry factor(glum)of-1.0 × 10-2 and+9.2 × 10-3,respectively.This work provides the useful evidences to reveal the induced chiral crystallization and the construction of CPL-active crystalline materials.

外文关键词：

Metal-organic frameworksCircularly polarized luminescenceChirality inductionSpontaneous resolutionChirality transfer

作者：

Hong-Ru Fu、Dan-Dan Ren、Kun Zhang、Hong Chen、Xiaoyan Lu、Qing-Rong Ding、Lu-Fang Ma

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作者单位：

College of Chemistry and Chemical Engineering,Luoyang Normal University,Luoyang,Henan 471934,China

State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences,Fuzhou,Fujian 350002,China

College of Materials & Chemical Engineering,China Three Gorges University,Yichang,Hubei 443002,China

基金：

National Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNatural Science Foundation for Excellent Young Scholars of Henan ProvinceNatural Science Foundation for Excellent Young Scholars of Henan ProvinceProgram for Innovative Research Team from the University of Henan ProvinceScience and Technology R&D Program of the Joint Funds of Henan ProvinceOpen Foundation of State Key Laboratory of Structural ChemistryScientific and Technological Support Project of Guizhou Province

项目编号：

221711232210206823230042108321230041006124IRTSTHN00522520081008220230021Qian Ke He Zhi Cheng[2023]Yi Ban 262

出版年：

2024

DOI：

10.1002/cjoc.202300645

中国化学(英文版)

中国化学会上海有机化学研究所

中国化学(英文版)

CSTPCD

影响因子：0.848

ISSN：1001-604X

年,卷(期)：2024.42(11)