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
Nikolaev Institute of Inorganic Chemistry, SB RAS, 3 Acad. Lavrentiev Ave., 630090, Novosibirsk, Russian Federation.
Voevodsky Institute of Chemical Kinetics and Combustion, SB RAS, 3 Institutskaya Str., 630090, Novosibirsk, Russian Federation.
Angew Chem Int Ed Engl. 2021 May 25;60(22):12577-12584. doi: 10.1002/anie.202103037. Epub 2021 Apr 22.
The first example of a triply bridging (μ -P) phosphine ligand has been discovered in the crown-shaped [Cu (μ -Hal) L] (Hal=Cl, Br, or I) complexes supported by tris[2-(2-pyridyl)ethyl]phosphine (L). Theoretical analysis completely confirms the observed μ -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 =442-465 nm) with the quantum efficiency reaching 100 %. The complex [Cu (μ -I) 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.
在由三[2-(2-吡啶基)乙基]膦（L）支撑的冠状[Cu(μ-Hal)L]（Hal = Cl、Br或I）配合物中发现了首例三桥联（μ-P）膦配体。理论分析完全证实了观察到的μ-P桥联模式，揭示了磷的同一孤对电子与三个铜原子的4s价轨道之间的相互作用。所呈现的配合物表现出出色的蓝色磷光（λ = 442 - 465 nm），量子效率达到100%。配合物[Cu(μ-I)L]还表现出显著的热致和机械致变色发光，在外部刺激下发射颜色会发生急剧变化。这些发现对磷系配体的配位化学做出了重要贡献。
