Jump to main content
Jump to site search


Terahertz time-domain absorption spectra of Cu(i) complexes bearing tetraphosphine ligands: the bridge between the C–H⋯π and π⋯π interactions and photoluminescence properties

Author affiliations

Abstract

The synthesis of four heteroleptic dinuclear Cu(I) complexes bearing tetraphosphine and diimine ligands was reported. Complexes 1–3 were successfully obtained through microwave synthesis while complex 4 was synthesized through traditionally stirring at room temperature. These complexes are listed as follows: [Cu2(Dpq)2(dppeda)](ClO4)2·1.5CH2Cl2 (1), [Cu2(neo)2(dppeda)](ClO4)2·1.3CH2Cl2·1.7C4H10O (2), [Cu2(batho)2(dppeda)](ClO4)2·C4H10O (3), and [Cu2(batho)2(dpppda)](ClO4)2·3CH2Cl2 (4) {(Dpq = pyrazino[2,3-f][1,10]phenanthroline, batho = 4,7-diphenyl-1,10-phenanthroline, neo = 2,9-dimethyl-1,10-phenanthroline, dppeda = N1,N1,N2,N2-tetrakis[(diphenylphosphino)methyl]-1,2-ethanediamine, and dpppda = N1,N1,N4,N4-tetrakis[(diphenylphosphino)methyl]-1,4-benzenediamine}. Their crystal structures have been elucidated by X-ray crystallography and their photophysical properties have been investigated in detail. Photophysical studies and time domain density functional theory (TD-DFT) calculations show that the luminescence performance of these four complexes is ascribed to metal-to-ligand charge transfer (MLCT) mixed with ligand-to-ligand charge transfer (LLCT), and complex 2 shows green emission at 574 nm with the highest quantum yield of up to 52.80%. In addition, the research of photoluminescence properties under the guidance of terahertz spectroscopy technology leads to the preliminary discovery of a correlation between crystal packing and luminescence. It is found that the terahertz spectrum and absorption peak are strongly interdependent on C–H⋯π and π⋯π interactions, and the external weak interactions have negative effects on the luminescence performance. Herein, we predict that the terahertz spectroscopy analysis establishes a bridge between weak interactions (C–H⋯π and π⋯π interactions) and the photoluminescence properties, and puts forward a problem that should be noticed in designing Cu(I) complexes.

Graphical abstract: Terahertz time-domain absorption spectra of Cu(i) complexes bearing tetraphosphine ligands: the bridge between the C–H⋯π and π⋯π interactions and photoluminescence properties

Back to tab navigation

Supplementary files

Article information


Submitted
19 Jul 2020
Accepted
29 Sep 2020
First published
30 Sep 2020

Dalton Trans., 2020, Advance Article
Article type
Paper

Terahertz time-domain absorption spectra of Cu(I) complexes bearing tetraphosphine ligands: the bridge between the C–H⋯π and π⋯π interactions and photoluminescence properties

X. Pan, X. Kuang, N. Zhu, G. Wang, Y. Yang, J. Liu, Z. Li, X. Xin, H. Han, Q. Jin, Z. Ren and J. Zhang, Dalton Trans., 2020, Advance Article , DOI: 10.1039/D0DT02542A

Social activity

Search articles by author

Spotlight

Advertisements