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Beyond Classical Coordination Chemistry: The First Case of a Triply Bridging Phosphine Ligand
Ist Teil von
Angewandte Chemie International Edition, 2021-05, Vol.60 (22), p.12577-12584
Auflage
International ed. in English
Ort / Verlag
Germany: Wiley Subscription Services, Inc
Erscheinungsjahr
2021
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
The first example of a triply bridging (μ3‐P) phosphine ligand has been discovered in the crown‐shaped [Cu3(μ2‐Hal)3L] (Hal=Cl, Br, or I) complexes supported by tris[2‐(2‐pyridyl)ethyl]phosphine (L). Theoretical analysis completely confirms the observed μ3‐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 (λem=442–465 nm) with the quantum efficiency reaching 100 %. The complex [Cu3(μ2‐I)3L] 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.
Phosphines are notorious in acting exclusively as terminal donors, binding a single metal center. We have discovered that a non‐traditional scenario is possible where the phosphorus(III) atom of a R3P ligand bridges three metal atoms at once. Such triply bridging pattern is first observed in the [Cu3(μ2‐Hal)3L] (Hal=Cl, Br, or I) complexes, which also exhibit remarkable luminescence properties.