Beyond Classical Coordination Chemistry: The First Case of a Triply Bridging Phosphine Ligand.

Authors :: Baranov AY
Pritchina EA
Berezin AS
Samsonenko DG
Fedin VP
Belogorlova NA
Gritsan NP
Artem'ev AV
Source :: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2021 May 25; Vol. 60 (22), pp. 12577-12584. Date of Electronic Publication: 2021 Apr 22.
Publication Year :: 2021
Abstract: The first example of a triply bridging (μ <subscript>3</subscript> -P) phosphine ligand has been discovered in the crown-shaped [Cu <subscript>3</subscript> (μ <subscript>2</subscript> -Hal) <subscript>3</subscript> L] (Hal=Cl, Br, or I) complexes supported by tris[2-(2-pyridyl)ethyl]phosphine (L). Theoretical analysis completely confirms the observed μ <subscript>3</subscript> -P-bridging pattern, revealing the interaction of the same lone pair of phosphorus with three valence 4s-orbitals of Cu atoms. The presented complexes exhibit outstanding blue phosphorescence (λ <subscript>em</subscript> =442-465 nm) with the quantum efficiency reaching 100 %. The complex [Cu <subscript>3</subscript> (μ <subscript>2</subscript> -I) <subscript>3</subscript> L] also exhibits remarkable thermo- and mechanochromic luminescence resulting in a sharp change in the emission colour upon external stimuli. These findings essentially contribute to coordination chemistry of the pnictine ligands.<br /> (© 2021 Wiley-VCH GmbH.)

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