Copper(I) Alkynyl Clusters with Crystallization Induced Emission Enhancement
Jun-Jie Fang, Yang-Lin Shen, Zheng Liu, Chen Liu, Yun-Peng Xie,* and Xing Lu*
Inorg. Chem., 2021.
https://doi.org/10.1021/acs.inorgchem.1c01829
Abstract
Four copper(I) alkynyl complexes incorporating phosphate ligands, namely,[Cu16 (tBuCC)12 (PhOPO3) 2]n (1; PhOPO3 = phenyl phosphate), [Cu16 (tBuCC)12 (1-NaphOPO3) 2]n (2; 1-NaphOPO 3 = 1-naphthyl phosphate), [VO4@Cu 25 (tBuCC)19(1-NaphOPO 3 )](PF 6 ) 0.5 (F) 0.5 (3), and [PO 4 @Cu 25 (tBuCC) 19 (1-NaphOPO 3 )]-(PF 6 ) 0.5 (F) 0.5 (4), were solvothermally synthesized and well-characterized by IRspectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Single-crystalX-ray analysis revealed that the Cu 16 cluster-based coordination chain polymers 1 and 2 areformed by assembly during crystallization, while 3 and 4 contain high-nuclearity copper(I)composite clusters enclosing orthovanadate and phosphate template ions, respectively, thatare supported by ROPO 32− ligands. Complexes 1−4 exhibit crystallization-inducedemission enhancement. Their crystalline state shows strong luminescence, in strikingcontrast to the weak emission of the amorphous state and solution phase. A detailedinvestigation of the crystal structure suggests that well-arranged C−H···π and π···πinteractions between the ligands are the major factors for this enhanced emission. Clusters 3 and 4 also exhibit photocurrentresponses upon visible-light illumination.
