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Copper(I) Alkynyl Clusters with Crystallization-Induced Emission Enhancement
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-08-19 , DOI: 10.1021/acs.inorgchem.1c01829
Jun-Jie Fang 1 , Yang-Lin Shen 1 , Zheng Liu 1 , Chen Liu 1 , Yun-Peng Xie 1 , Xing Lu 1
Affiliation  

Four copper(I) alkynyl complexes incorporating phosphate ligands, namely, [Cu16(tBuC≡C)12(PhOPO3)2]n (1; PhOPO3 = phenyl phosphate), [Cu16(tBuC≡C)12(1-NaphOPO3)2]n (2; 1-NaphOPO3 = 1-naphthyl phosphate), [VO4@Cu25(tBuC≡C)19(1-NaphOPO3)](PF6)0.5(F)0.5 (3), and [PO4@Cu25(tBuC≡C)19(1-NaphOPO3)](PF6)0.5(F)0.5 (4), were solvothermally synthesized and well-characterized by IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Single-crystal X-ray analysis revealed that the Cu16 cluster-based coordination chain polymers 1 and 2 are formed by assembly during crystallization, while 3 and 4 contain high-nuclearity copper(I) composite clusters enclosing orthovanadate and phosphate template ions, respectively, that are supported by ROPO32– ligands. Complexes 14 exhibit crystallization-induced emission enhancement. Their crystalline state shows strong luminescence, in striking contrast to the weak emission of the amorphous state and solution phase. A detailed investigation of the crystal structure suggests that well-arranged C–H···π and π···π interactions between the ligands are the major factors for this enhanced emission. Clusters 3 and 4 also exhibit photocurrent responses upon visible-light illumination.

中文翻译:

具有结晶诱导发射增强的铜 (I) 炔基团簇

四种结合磷酸盐配体的铜 (I) 炔基配合物,即 [Cu 16 ( t BuC≡C) 12 (PhOPO 3 ) 2 ] n ( 1 ; PhOPO 3 = 苯基磷酸酯), [Cu 16 ( t BuC≡C) 12 (1-NaphOPO 3 ) 2 ] n ( 2 ; 1-NaphOPO 3 = 1-萘基磷酸酯), [VO 4 @Cu 25 ( t BuC≡C) 19 (1-NaphOPO 3 )](PF 6 ) 0.5 (F) )0.5 ( 3 ) 和 [PO 4 @Cu 25 ( t BuC≡C) 19 (1-NaphOPO 3 )](PF 6 ) 0.5 (F) 0.5 ( 4 ) 是溶剂热合成的,并通过红外光谱表征,粉末 X 射线衍射和单晶 X 射线衍射。单晶 X 射线分析表明,Cu 16簇基配位链聚合物12是在结晶过程中通过组装形成的,而34包含分别包围原钒酸盐和磷酸盐模板离子的高核铜(I)复合簇,由 ROPO 3 2–配体支持。配合物1 - 4表现出结晶诱导发射增强。它们的结晶状态显示出强烈的发光,与非晶态和溶液相的弱发射形成鲜明对比。对晶体结构的详细研究表明,配体之间排列良好的 C-H···π 和 π···π 相互作用是这种增强发射的主要因素。簇34在可见光照射下也表现出光电流响应。
更新日期:2021-09-06
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