Citation: SUN Zhen-Zhou, SUN Ling-Zhi, ZHU Ning, KUANG Xiao-Nan, YANG Yu-Ping, LI Zhong-Feng, JIN Qiong-Hua, ZHANG Jiang-Wei. Syntheses, Crystal Structures and Terahertz Spectra of Two Copper(Ⅰ) Complexes Based on Mixed Diimines and Diphosphine Ligands[J]. Chinese Journal of Inorganic Chemistry, ;2020, 36(12): 2261-2270. doi: 10.11862/CJIC.2020.251 shu

Syntheses, Crystal Structures and Terahertz Spectra of Two Copper(Ⅰ) Complexes Based on Mixed Diimines and Diphosphine Ligands

1.
Department of Chemistry, Capital Normal University, Beijing 100048, China
2.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
3.
School of Science, Minzu University of China, Beijing 100081, China
4.
Dalian National Laboratory for Clean Energy & State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences(CAS), Dalian, Liaoning 116023, China

Corresponding author: JIN Qiong-Hua, jinqh@cnu.edu.cn ZHANG Jiang-Wei, jwzhang@dicp.ac.cn
Received Date: 30 March 2020
Revised Date: 8 September 2020

Figures(9)

Two copper (Ⅰ) complexes with diimine and diphosphine ligands, [Cu₂(Dpq)₂(dppBz)₂] (SCN)₂·0.5Dpq·3CH₃OH (1) and [Cu₂(Dppz)₂(dppb)₂](BF₄)₂·2CH₃OH·2H₂O (2) (Dppz=dipyrido[3, 2-a:2', 3'-c]phenazine, Dpq=pyrazino[2, 3-f]^{[1, 10]}phenanthroline, dppBz=1, 2-bis(diphenylphosphino)benzene, dppb=1, 3-bis(diphenylphosphine)butane), were prepared in the mixed solution of methanol and dichloromethane. The structure of these two complexes were determined by X-ray single crystal diffraction and characterized by elemental analysis, NMR, FT-IR, UV-Vis absorption spectrum, fluorescence spectrum and terahertz time-domain spectroscopy (THz-TDS). The unit cell of 1 contains two independent metal centers and half uncoordinated Dpq molecule, and similar structures are very rare. However, complex 2 are novel binuclear structure formed by the bisphosphine ligand. Through the analysis of intermolecular forces, 1 is a three-dimensional stacked structure, which contains unique C-S…π interactions. But 2 forms one-dimensional infinite chain through C-H…π and π…π. The existence of a large number of weak interactions makes the complexes more stable. The emission spectra showed that the peak of complex 1 was at 578 nm, however, complex 2 emitted green light (at 547 nm). The sharp peak at 1.2 THz in THz-TDS spectrum of complex 2 is caused by the interactions of C-H…F.CCDC: 1991845, 1; 1991844, 2.
- copper (Ⅰ) complexes,
- fluorescence,
- intermolecular force,
- terahertz time-domain spectroscopy
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