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
Thermo-responsive microcrystals exhibiting obvious emission intensity or color changes have great potentials in sensing,information encryption,and microelectronics.We report herein the binary assembly of a blue-emissi...Thermo-responsive microcrystals exhibiting obvious emission intensity or color changes have great potentials in sensing,information encryption,and microelectronics.We report herein the binary assembly of a blue-emissive iridium complex and a red-emissive ruthenium complex into homogeneously-doped or optically-heterostructured microcrystals with thermo-responsive properties.Depending on the assembly conditions,lateral or longitudinal triblock heterostructures with a microplate shape are obtained,which display distinct emission pattern changes upon heating as a result of the decreased efficiency of energy transfer.In addition,branched heterostructures are prepared by a stepwise assembly.The luminescence polarization of the homogeneously-doped binary crystals and the waveguiding property of the longitudinal triblock heterostructure are further examined.This work evidences the versatility of transition metal complexes in the assembly into various luminescent nano/micro structures with potential applications in thermo-sensing and nanophotonics.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.
基金the National Key R&D Program of China(No.2023YFE0125200)National Natural Science Foundation of China(Nos.21925112 and 22090021)for funding support.
文摘Thermo-responsive microcrystals exhibiting obvious emission intensity or color changes have great potentials in sensing,information encryption,and microelectronics.We report herein the binary assembly of a blue-emissive iridium complex and a red-emissive ruthenium complex into homogeneously-doped or optically-heterostructured microcrystals with thermo-responsive properties.Depending on the assembly conditions,lateral or longitudinal triblock heterostructures with a microplate shape are obtained,which display distinct emission pattern changes upon heating as a result of the decreased efficiency of energy transfer.In addition,branched heterostructures are prepared by a stepwise assembly.The luminescence polarization of the homogeneously-doped binary crystals and the waveguiding property of the longitudinal triblock heterostructure are further examined.This work evidences the versatility of transition metal complexes in the assembly into various luminescent nano/micro structures with potential applications in thermo-sensing and nanophotonics.
