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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 international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202103037
Subject(s) - phosphine , lone pair , phosphorescence , bridging (networking) , chemistry , luminescence , bridging ligand , atomic orbital , crystallography , coordination complex , ligand (biochemistry) , valence (chemistry) , quantum chemistry , photochemistry , stereochemistry , molecule , crystal structure , materials science , organic chemistry , electron , metal , fluorescence , supramolecular chemistry , physics , receptor , catalysis , computer network , biochemistry , optoelectronics , quantum mechanics , computer science
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.