Planar Chiral[2.2]Paracyclophane-Based Zr(IV)Metal-Organic Frameworks  

作　　者：Hong Jiang Wenqiang Zhang Bang Hou Yan Liu Yong Cui 

机构地区：[1]School of Chemistry and Chemical Engineering,Frontiers Science Center for Transformative Molecules,State Key Laboratory of Metal Matrix Composites,Shanghai Jiao Tong University,Shanghai 200240

出　　处：《CCS Chemistry》2023年第7期1635-1643,共9页中国化学会会刊（英文）

基　　金：This work was financially supported by the National Natural Science Foundation of China(grant nos.21620102001,91856204,91956124,and 21875136);Key Project of Basic Research of Shanghai(grant no.19JC1412600);Shanghai Rising-Star Program(grant no.19QA1404300),and the China Postdoctoral Science Foundation(grant no.2020M681280).

摘　　要：Self-assembly has been widely explored to improve the circularly polarized_(lum)inescence(CPL)activities of molecular chromophores,but it is hard to amplify CPL while maintaining strong emissions.Optically pure,planar-chiral[2.2]paracyclophane(pCp)is one of the most important sources of chirality for electronic and optoelectronic materials,but the photo_(lum)inescence of its derivatives is significantly quenched after forming aggregates.Here we demonstrate that reticulation of pCp chromophores into highly stable Zr(IV)metal-organic frameworks(MOFs)can simultaneously boost the dissymmetry factor(|g_(lum)|)and_(lum)inescence efficiency(Φ_(PL)).Functionalization of pCp enables the synthesis of two tetracarboxylate linkers with different side arms,which are assembled into two highly stable Zr-MOFswith different topological structures.Geometrical constraints and segregated arrangements of the pCp chromophores imposed by the framework inhibit the aggregation-caused quenching effect and boost their CPL behaviors.Both Zr-MOFs display strong CPL emissions,affording|g_(lum)|andΦ_(PL)values of up to 8.3×10^(-3)and 87%,respectively,which are amplified by∼18-and 52-fold compared to the corresponding free ligands.This work highlights the potential of optimizing CPL performances of chiral chromophores by using MOFs as support structures.

关 键 词：metal-organic frameworks circularly polarized luminescence planar chirality quantumyield dissymmetric factor 

分 类 号：O62[理学—有机化学]