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Issue 43, 2020

Photoluminescent properties and molecular structures of dinuclear gold(i) complexes with bridged diphosphine ligands: near-unity phosphorescence from 3XMMCT/3MC

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Abstract

The gold(I) complexes [μ-LiPr(AuX)2] {X = Cl (1D), Br (2D), and I (3D); LiPr = 1,2-bis[bis(2-isopropylphenyl)phosphino]benzene} were synthesised to investigate the photoluminescence properties of dinuclear Au complexes comprising weak Au(I)–Au(I) bonds. Single crystals of the tetrahydrofuran (THF) adducts 1DOR, 2DOR, and 3DOR were obtained by recrystallisation of 1D, 2D, and 3D from a mixed solution of THF and n-hexane. These THF adducts afford orange emission, with peak wavelengths ranging from 597 to 630 nm, in the crystalline state at 293 K. Recrystallisation of 3D from a mixed solution of acetone and n-hexane afforded single crystals of the acetone adduct 3DGR, which exhibits blue-green emission at 293 K. No crystals of the acetone adduct were obtained from 1D and 2D. The emission spectra and lifetimes of 1DOR, 2DOR, 3DOR, and 3DGR measured in the temperature range 77–293 K indicate that emission from these complexes in the solid state is due to phosphorescence. Notably, although the molecular structure of 3D in the 3DOR crystal is near-similar to that of 3DGR, the phosphorescence spectrum of 3DOR differs markedly from that of 3DGR, with peak wavelengths at 597 and 506 nm, respectively. Theoretical studies revealed that (1) phosphorescence occurs via the electronic transition from the excited triplet state, which is mainly composed of halogen-to-metal–metal charge transfer and metal-centered transitions and (2) the T1-optimised structure of 3D in the 3DGR crystals differs markedly from that in 3DOR, and the differences in the phosphorescence colour observed between 3DGR and 3DOR are ascribed to the differences in their stabilised structures in the excited triplet state.

Graphical abstract: Photoluminescent properties and molecular structures of dinuclear gold(i) complexes with bridged diphosphine ligands: near-unity phosphorescence from 3XMMCT/3MC

Supplementary files

Article information


Submitted
08 Sep 2020
Accepted
01 Oct 2020
First published
07 Oct 2020

Dalton Trans., 2020,49, 15204-15212
Article type
Paper

Photoluminescent properties and molecular structures of dinuclear gold(I) complexes with bridged diphosphine ligands: near-unity phosphorescence from 3XMMCT/3MC

M. Osawa, S. Soma, M. Hoshino, Y. Tanaka and M. Akita, Dalton Trans., 2020, 49, 15204 DOI: 10.1039/D0DT03144E

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