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 ...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.展开更多
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(NSFCgrant nos.21925112 and 22090021).
文摘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.
