Spontaneous Symmetry Breaking of Iridium and Ruthenium Metallophosphors for the Constructions of Chiral Light-Harvesting Systems  

作　　者：Chun-Yun Ding Yu-Wu Zhong Jiannian Yao 

机构地区：[1]Beijing National Laboratory for Molecular Sciences,CAS Key Laboratory of Photochemistry,CAS Research/Education Center for Excellence in Molecular Sciences,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190 [2]School of Chemical Sciences,University of Chinese Academy of Sciences,Beijing 100049

出　　处：《CCS Chemistry》2024年第11期2713-2726,共14页中国化学会会刊（英文）

基　　金：a result of a generous grant from the National Key R&D Program of China(grant no.2023YFE0125200);the National Natural Science Foundation of China(NSFC;grant nos.21925112 and 22090021).

摘　　要：Symmetry breaking for chirality generation and lightharvesting for solar energy conversion are two momentous topics in natural systems.The construction of a chiral light-harvesting system completely based on symmetry breaking is a formidable challenge.Here,we report the spontaneous chiral symmetry breaking(CSB)of two iridium and ruthenium metallophosphors(IrD and RuA)with the assistance of achiral solvents.The subtle noncovalent intermolecular interactions between complexes and polar solvents play a vital role in the crystallization of homochiral molecules and the resulting CSB.Utilizing a molecular doping strategy,transferred,ampli-fied,and inverted circularly polarized luminescence(CPL)was achieved in the binary microcrystals(MCs)composed of chiral/achiral IrD and achiral/chiral RuA,with large dissymmetry factors(glum,up to 0.06)and enhanced emission quantum yields(over 35%).The use of only 0.05%of chiral RuA in the lattice of achiral IrD led to the chiral amplification with glum of 1×10−2 and morphology transition,while inverted and white CPL were obtained in MCs containing monodispersed chiral RuA in the lattice cavities of another polymorphic crystal of IrD.Diffuse reflection circular dichroism measurements gave information on the chirality transfer mechanisms behind these spin-related chiroptical properties.

关 键 词：chiral symmetry breaking metallophosphors circularly polarized luminescence chirality transfer energy transfer chirality amplification 

分 类 号：O62[理学—有机化学]