Luminescent ionic heterobimetallic diphosphine-β-diketiminate complexes

Abstract

The syntheses of luminescent heterobimetallic ionic complexes based on the bis(phosphine)-functionalized β-diketiminate ligand [HC{(CH3)C}2{(o-[P(C6H5)2]2C6H4)N}2] (PNac) are reported. This orthogonal ligand is characterized by its PNNP pocket, which contains both hard and soft donor sites and therefore enables the selective coordination of two different metal ions in spatial proximity, significantly changing the photoluminescent properties. Salt elimination reaction of [PNacK] with zinc chloride yields the monometallic complex [PNacZnCl], in which the zinc ion is square-pyramidally coordinated within the PNNP pocket. The introduction of the coinage metal ions AuI, AgI and CuI into the PNNP pocket as a second metal ion is achieved by simple complexation reactions using their corresponding weakly coordinating anion (WCA) salts. In the resulting ionic heterobimetallic complexes [PNacZnCl(thf)M]+ (M = Au, Ag, and Cu), the coinage metal ions are linearly coordinated by the two phosphine units, while the zinc ion is tetrahedrally coordinated at the diketiminate unit. The photoluminescent properties are significantly altered by the spatial proximity of the two metal ions. Furthermore, the ionic gold–copper complex [PNacAuCu(MeCN)]+ was isolated by introducing CuI into the monometallic gold complex using the same method.

Graphical abstract: Luminescent ionic heterobimetallic diphosphine-β-diketiminate complexes

Supplementary files

Article information

Article type
Paper
Submitted
25 Apr 2025
Accepted
27 Jul 2025
First published
18 Aug 2025
This article is Open Access
Creative Commons BY license

Dalton Trans., 2025, Advance Article

Luminescent ionic heterobimetallic diphosphine-β-diketiminate complexes

S. Kebernik, F. Krätschmer, X. Sun and P. W. Roesky, Dalton Trans., 2025, Advance Article , DOI: 10.1039/D5DT00977D

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