Premium
Beyond Classical Coordination Chemistry: The First Case of a Triply Bridging Phosphine Ligand
Author(s) -
Baranov Andrey Y.,
Pritchina Elena A.,
Berezin Alexey S.,
Samsonenko Denis G.,
Fedin Vladimir P.,
Belogorlova Nataliya A.,
Gritsan Nina P.,
Artem'ev Alexander V.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202103037
Subject(s) - phosphine , chemistry , phosphorescence , lone pair , luminescence , bridging ligand , bridging (networking) , coordination complex , atomic orbital , crystallography , ligand (biochemistry) , quantum chemistry , valence (chemistry) , photochemistry , crystal structure , molecule , supramolecular chemistry , materials science , catalysis , organic chemistry , metal , electron , fluorescence , optoelectronics , quantum mechanics , computer science , computer network , biochemistry , physics , receptor
The first example of a triply bridging (μ 3 ‐P) phosphine ligand has been discovered in the crown‐shaped [Cu 3 (μ 2 ‐Hal) 3 L] (Hal=Cl, Br, or I) complexes supported by tris[2‐(2‐pyridyl)ethyl]phosphine (L). Theoretical analysis completely confirms the observed μ 3 ‐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 em =442–465 nm) with the quantum efficiency reaching 100 %. The complex [Cu 3 (μ 2 ‐I) 3 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.