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Zhang, Xi; Song, Jia‐Xi; Chang, Xiaoyong; Li, Kai; Chen, Yong
Chemistry : a European journal, May 2, 2024, Volume: 30, Issue: 25Journal Article
Copper(I)‐based thermally activated delayed fluorescence (TADF) emitters have been conceived to be promising candidates for display and lighting applications because of their multifarious structures and strong photoluminescence. Herein a string of binuclear Cu(I) complexes bearing pronounced cuprophilic interactions have been designed and synthesized. Cu2(dppb)2(μ2‐η1‐C≡C−Ph)2 (1 a) and Cu2(dppb)2(μ2‐η1‐C≡C−PPXZ)2 (1 b) display photoluminescence quantum yields of up to 67 % in doped films and solid states via TADF and exhibit reversible bicolor luminescence switching upon mechanical stimuli. Computational studies manifest that the metal‐to‐ligand charge transfer predominant transitions ensure a small energy splitting (ΔEST) between the lowest singlet (S1) and triplet (T1) excited states and cuprophilic interactions promote the spin‐orbit coupling (SOC), favoring the reverse intersystem crossing (RISC) process. This study provides a new strategy for the construction of stimuli‐responsive metal‐based TADF materials. Binuclear copper(I) alkynyl complexes with ultrashort Cu−Cu distance are designed and synthesized, which show thermally activated delayed fluorescence (TADF) and mechanochromic luminescence (MCL). The cuprophilic interactions can promote spin‐orbit coupling and ligand engineering can achieve adjustable luminescence, which provide design ideas for the building of stimuli‐responsive Cu(I)‐based TADF materials.
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