Near-unity thermally activated delayed fluorescence efficiency in three- and four-coordinate Au(i) complexes with diphosphine ligands

Dalton Transactions : an International Journal of Inorganic Chemistry
Masahisa OsawaMunetaka Akita

Abstract

The synthesis and photoluminescence properties of three-coordinate Au(i) complexes with rigid diphosphine ligands LMe {1,2-bis[bis(2-methylphenyl)phosphino]benzene}, LEt {1,2-bis[bis(2-ethylphenyl)phosphino]benzene}, and LiPr {1,2-bis[bis(2-isopropylphenyl)phosphino]benzene} are investigated. The LMe and LEt ligands afford two types of complexes: dinuclear complexes [μ-LMe(AuCl)2] (1d) and [μ-LEt(AuCl)2] (2d) with an Au(i)-Au(i) bond and mononuclear three-coordinate Au(i) complexes LMeAuCl (1) and LEtAuCl (2). On the other hand, the bulkiest ligand, LiPr, affords three-coordinate Au(i) complexes, LiPrAuCl (3) and LiPrAuI (4), but no dinuclear complexes. X-ray analysis suggests that both 3 and 4 possess a highly distorted trigonal planar geometry. Moreover, luminescence data reveal that at room temperature, 3 and 4 exhibit yellow-green thermally activated delayed fluorescence in the crystalline state with maximum emission wavelengths at 558 and 549 nm, respectively. The emission yields are close to unity. Quantum chemical calculations suggest that the emission of 4 originates from the (σ + X) → π* excited state that possesses strong intraligand charge-transfer character. The luminescent properties of four-coordinate Au(i) comple...Continue Reading

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Citations

Jan 11, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Ji-Hui JiaCan-Zhong Lu
Nov 11, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Masahisa OsawaMunetaka Akita
Aug 12, 2021·Chemistry, an Asian Journal·Xiaoning LiZhen Li
Feb 26, 2020·Inorganic Chemistry·Lucy M C LuongAlan L Balch

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Methods Mentioned

BETA
phosphorescence
NMR
X-ray

Software Mentioned

TD
DFT

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