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Structural relaxation chirality transfer enhanced circularly polarized luminescence in heteronuclear CeIII-MnII
Huanyu Liu1, Gang Yu1, Peihao Huo1
1Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China. zwliu@pku.edu.cn.
Abstract:
Circularly polarized luminescence (CPL) materials have developed rapidly in recent years due to their wide application prospects in fields like 3D displays and anti-counterfeiting. Utilizing energy transfer processes to transfer chirality has been proven as an efficient way to obtain CPL materials. However, the physics behind energy-transfer induced CPL is still not clear. Herein, in a well-designed heteronuclear CeIII-MnII complex system [(Ce((R/S)-L)Br(μ-Br))2]MnBr4 [(R/S)-L = (2R,3R)- or (2S,3S)-2,3-dimethyl-1,4,7,10,13,16-hexaoxacyclooctadecane] with intra energy transfer from CeIII to MnII, the luminescence dissymmetry factor of MnII obtained by excitation of CeIII is around 10 times higher than that obtained by direct excitation of MnII, while the CeIII center itself shows an almost negligible CPL. To address this unusual phenomenon, we proposed a new mechanism named structural relaxation chirality transfer (SRCT) where structural relaxation of the excited chiral donor amplified chirality transfer to the acceptor by intramolecular interactions. As an assistant proof, a mixture of CeIII-ZnII and LaIII-MnII complexes with inter energy transfer showed no CPL amplification. These results will inspire more breakthroughs in the physics nature and development of energy-transfer induced CPL.
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