Issue 47, 2021

A series of luminescent Cu(i) complexes based on the diphosphine ligand and diimine ligand: weak intermolecular interactions, terahertz spectroscopy and photoproperties

Abstract

Five novel mononuclear [Cu(Bphen)(bdppmapy)]X complexes showing photoluminescence were synthesized. The same diphosphine ligand and diimine ligand and different Cu(I) salts were used in the one-pot synthesis of complexes 1–5. These complexes are listed as follows: [Cu(Bphen)(bdppmapy)]CF3SO3 (1), [Cu(Bphen)(bdppmapy)]BF4·0.268CH3OH (2), [Cu(Bphen)(bdppmapy)]ClO4 (3), [Cu(Bphen)(bdppmapy)]I·CH3OH (4) and [Cu(Bphen)(bdppmapy)]Br·2CH3OH (5) (Bphen = 4,7-diphenyl-1,10-phenanthroline, bdppmapy = N,N-bis((diphenylphosphino)methyl)-2-pyridinamine). IR, NMR, elemental analysis, single-crystal X-ray diffraction analysis, UV-vis, fluorescence spectroscopy and terahertz time-domain absorption spectroscopy (THz-TDS) were used to characterize 1–5. Their crystal structures have been elucidated by X-ray crystallography and their photophysical properties have been investigated in detail. These five complexes have a similar coordination center, while their space stacked structures are different, from a 0D dimeric structure to a 3D supramolecular structure. Photophysical studies and density functional theory calculations (DFT) show that the luminescence properties of these five complexes are mainly ascribed to metal-to-ligand charge transfer (MLCT). Among these five complexes, 1 emits luminescence with the highest quantum yield of 36.96% and a lifetime of 11.90 μs at ambient temperature. Different counter-anions lead to the distinction of QYs, maybe due to the influence of weak forces. Terahertz time-domain absorption spectroscopy was used to characterize these ligands and complexes in the range of 0.2–2.4 THz.

Graphical abstract: A series of luminescent Cu(i) complexes based on the diphosphine ligand and diimine ligand: weak intermolecular interactions, terahertz spectroscopy and photoproperties

Supplementary files

Article information

Article type
Paper
Submitted
21 Mha 2021
Accepted
09 Ndz 2021
First published
19 Nhl 2021

CrystEngComm, 2021,23, 8323-8333

A series of luminescent Cu(I) complexes based on the diphosphine ligand and diimine ligand: weak intermolecular interactions, terahertz spectroscopy and photoproperties

Z. Li, X. Kuang, G. Wang, N. Zhu, Z. Sun, H. Han, Y. Yang, Z. Li, X. Xin, Q. Jin and Z. Ren, CrystEngComm, 2021, 23, 8323 DOI: 10.1039/D1CE01132D

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