化学
发光
堆积
结晶学
量子产额
连接器
分子间力
产量(工程)
单晶
溶剂
4,4'-联吡啶
分子
荧光
氢键
有机化学
材料科学
物理
操作系统
量子力学
冶金
光电子学
计算机科学
作者
Atsushi Kobayashi,Masaru Fujii,Yasuhiro Shigeta,Masaki Yoshida,Masako Kato
出处
期刊:Inorganic Chemistry
[American Chemical Society]
日期:2019-03-13
卷期号:58 (7): 4456-4464
被引量:29
标识
DOI:10.1021/acs.inorgchem.8b03641
摘要
The luminescent Cu(I) coordination polymers [Cu2I2(m,m′-bpy)]n (CuI-m; m,m′-bpy = m,m′-bipyridine; m = 3, 4) were successfully synthesized by the solvent-free thermal reaction of the metal salt CuI with the organic linkers m,m′-bpy. Powder X-ray diffraction analysis revealed that CuI-3 was immediately formed when a mixture of CuI and 3,3′-bpy was ground in a mortar at room temperature (20 °C). In contrast, a temperature >120 °C was required to synthesize the CuI-4 isomer, probably because of the higher melting point of the 4,4′-bpy linker. Although excess bpy linker was necessary to afford the CuI-m in high yield, the quantitative synthesis, without any purification processes, was successfully achieved by simple heating at 140 °C, whereby the excess bpy linker was thermally removed by evaporation. Single crystal X-ray structural analysis indicated that in CuI-3 the dinuclear {Cu2I2} rhombic cores were bridged by 3,3′-bpy linkers. A similar structure was observed for CuI-4; however, the intermolecular π–π stacking that was effective in CuI-4 was suppressed in CuI-3 because of the twisted configuration of the two pyridyl rings of the 3,3′-bpy linker. CuI-3 exhibited bright green emission with the maximum (λem) at 519 nm and a high emission quantum yield (Φ = 0.58) in the solid state at room temperature, in contrast to the weak red emission of CuI-4 (λem = 653 nm, Φ < 0.01). Emission decay analysis and density functional theory calculations suggested that the CuI-m emissions could be attributed to the delayed fluorescence from the metal-to-ligand charge-transfer excited state effectively mixed with the halide-to-ligand charge-transfer excited state.
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