Supramolecular assemblies of multi-nuclear transition metal complexes: Synthesis and redox properties

• Published in: Coordination chemistry reviews Vol. 265; pp. 38 - 51
• Main Authors: Tanaka, Shinji, Tsurugi, Hayato, Mashima, Kazushi
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.04.2014
• Subjects: Cluster complexes; Coupling reaction of peripheral ligands; Redox property; Substitution reactions of linker ligands; Supramolecular metal complexes; Coupling reaction of peripheral ligands; dppa; DAniF; Supramolecular metal complexes; dppm; Redox property; py; DPhF; Cluster complexes; Substitution reactions of linker ligands; DArF
• ISSN: 0010-8545; 1873-3840
• DOI: 10.1016/j.ccr.2014.01.012

•Assemblies of multi-metallic complexes are classified by three reaction patterns.•Attractive redox behaviors of assembled transition metal complexes.•Controlled ligand substitutions of multi-nuclear transition metal complexes.•Metal-catalyzed coupling reactions of peripheral ligands. The synthetic features of supramolecular assemblies comprised of multi-nuclear transition metal complexes were reviewed by classification of the reaction patterns: (1) substitution reaction by bridging ligands, (2) substitution reaction by monodentate ligands, and (3) coupling reaction of functional groups attached to peripheral ligands. Architectural control for assembling multi-nuclear units is difficult because of the complicated ligand substitution reactions of metal clusters, but controlled ligand substitution of multi-metallic complexes recently became a targeted subject of coordination chemistry by introducing suitable bridging and monodentate ligands to keep multi-metallic entities intact, leading to the formation of 1D, 2D, and 3D supramolecules of multi-metallic units. Another synthetic protocol is aimed at transition metal-catalyzed coupling reactions of peripheral ligands that provide selective oligomerization of multi-metallic complexes. These supramolecules are of particular interest because of their unique redox properties centered at multi-metallic units, and their redox behaviors are described.