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

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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) complex (5) possessing a tetrahedral geometry are discussed on the basis of the emission spectra and decay times measured in a temperature range of 309–77 K.

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

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Publication details

The article was received on 22 Mar 2018, accepted on 02 May 2018 and first published on 05 May 2018


Article type: Paper
DOI: 10.1039/C8DT01097H
Citation: Dalton Trans., 2018, Advance Article
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    Near-unity thermally activated delayed fluorescence efficiency in three- and four-coordinate Au(I) complexes with diphosphine ligands

    M. Osawa, M. Aino, T. Nagakura, M. Hoshino, Y. Tanaka and M. Akita, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C8DT01097H

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