Thermally induced transformation of a Cu₄I₄-based cluster to a Cu₂I₂-based cluster under mild conditions

Abstract

A reaction of 6,6'-bis((benzylthio)methyl)-2,2'-bipyridine (L) with CuI at room temperature led to one Cu4I4-based cluster, which could be thermally transferred to Cu2I2-based one under mild condition due to the formation...

Emission and Luminescent Vapochromism Control of Octahedral Cu4I4 Complexes by Conformationally Restricted P,N Ligands

“…It should be mentioned that the “stretched” structure of Cu 4 I 4 core found for 2‐ACN and 2‐benzene is a new example of octahedral copper clusters [15,38,43,51] …”

“…It should be mentioned that the "stretched" structure of Cu 4 I 4 core found for 2-ACN and 2-benzene is a new example of octahedral copper clusters. [15,38,43,51] According to XRD-analysis, crystal solvates of complex 2 have the variable structure of the coordination sphere, including the expansion-contraction of Cu 4 I 4 core resulting in the Chemistry-A European Journal changing of the Cu-Cu distances (Tables S1), different orientation of the PÀ Cu and NÀ Cu coordination bonds relative to the Cu 4 -plane, which gives four structurally different conformers with different core geometry (Figure 6). Obtained structures generally can be separated into two types: "compact" (2-DCM and 2-acetone) and "stretched" (2-benzene and 2-ACN).…”

“…[27,35] The tetranuclear complexes are represented by structures with the stair-step, cubane-like, and octahedral Cu 4 I 4 metal-halide cores. [36][37][38][39][40][41][42][43][44][45] Cubane-like Cu 4 I 4 complexes often demonstrate the dual emission in the blue (high energy (HE) band) and yellow or red (low energy (LE) band) ranges of the spectrum. The reasons for the dual emission of cubane-like complexes are well studied and caused by the transitions from the two triplet states with metal-to-ligand charge transfer ( 3 MLCT or 3 (M + X)LCT) and cluster-centered ( 3 CC) origins.…”

“…Among various copper(I) structures tetranuclear complexes become promising candidates for the design of “stimuli‐responsive” emitters [27,35] . The tetranuclear complexes are represented by structures with the stair‐step, cubane‐like, and octahedral Cu 4 I 4 metal‐halide cores [36–45] …”