The synthesis and photophysical properties of two luminescent Cu^I coordination polymers, [Cu₂I₂(PPh₃)₂(3‐tpyb)]_n and [Cu₂I₂(PPh₃)₂(4‐tpyb)]_n (Cu‐3‐tpyb and Cu‐4‐tpyb; PPh₃=triphenylphosphine, m‐tpyb=1,3,5‐tris(m‐pyridyl)benzene (m=3, 4)), are described. X‐ray structural analysis indicated that one‐dimensional coordination chains comprising rhombic {Cu₂I₂(PPh₃)₂} cores and m‐tpyb bridging ligands were formed. Both Cu‐3‐tpyb and Cu‐4‐tpyb exhibited blue‐to‐yellow thermally activated delayed fluorescence (TADF) that originated from mixing of the metal‐to‐ligand and halide‐to‐ligand charge‐transfer excited states and moderate emission quantum yields of 0.29 and 0.27, respectively, at 298 K. Further, mechanochromic luminescence was observed for both complexes. The emission lifetimes indicated that the origin of emission switched from TADF to phosphorescence, which was derived from the triplet cluster‐centered (³CC) emissive state generated by grinding‐induced amorphization.

中文翻译：

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碘化铜（I）菱形菱形核组成的配位聚合物的延迟荧光与磷光之间的机械变色切换

两种发光的Cu ^I配位聚合物[Cu ₂ I ₂（PPh ₃）₂（3-tpyb）] _n和[Cu ₂ I ₂（PPh ₃）₂（4-tpyb）] _n（Cu ‐‐3‐tpyb和Cu‐4‐tpyb ; PPh ₃ =三苯膦，m ‐tpyb = 1,3,5‐tris（m‐吡啶基）苯（m = 3，4））。X射线结构分析表明，一维配位链包括菱形{Cu ₂ I ₂（PPh ₃）₂ }核和m- tpyb桥联配体形成。两个铜-3- tpyb和铜-4- tpyb呈现蓝色到黄色的热活化延迟荧光（TADF）源自电荷转移激发态和较低的排放的金属-配体和混合配位体卤化物到298 K时的量子产率分别为0.29和0.27。此外，两种配合物均观察到了机械致变色发光。发射寿命表明，发射的起源从TADF转换为磷光，这是由研磨诱导的非晶化产生的三重态团簇中心（³ CC）发射态得出的。