Mechanochromic Switching between Delayed Fluorescence and Phosphorescence of Luminescent Coordination Polymers Composed of Dinuclear Copper(I) Iodide Rhombic Cores
Mechanochromic Switching between Delayed Fluorescence and Phosphorescence of Luminescent Coordination Polymers Composed of Dinuclear Copper(I) Iodide Rhombic Cores
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DOI：
10.1002/chem.201802532
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发表时间：
2018-10-01
影响因子：
4.3
通讯作者：
Kato, Masako
中科院分区：
文献类型：
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作者：
Kobayashi, Atsushi;Yoshida, Yuya;Kato, Masako
描述了两种发光Cu-I配位聚合物[Cu2I2(PPh3)(2)(3-tpyb)](n)和[Cu2I2(PPh3)(2)(4-tpyb)](n) （Cu-3-tpyb和Cu-4-tpyb； PPh3=三苯基膦，m-tpyb=1,3,5-三（m-吡啶基）苯（m= 3,4））的合成及其光物理性质。x射线结构分析表明，形成了由菱形{Cu2I2(PPh3)(2)}核和m-tpyb桥接配体组成的一维配位链。Cu-3-tpyb和Cu-4-tpyb均表现出蓝到黄的热激活延迟荧光（TADF），这是由金属到配体和卤化物到配体的电荷转移激发态混合产生的，在298K时，发射量子产率分别为0.29和0.27。此外，还观察到这两种配合物的机械致色发光。发射寿命表明，发射源由TADF转变为磷光，这是由磨削诱导非晶化产生的三重态团簇中心（(CC)-C-3）发射态引起的。
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 298K. 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 ((CC)-C-3) emissive state generated by grinding-induced amorphization.