Photoinduced Self‐assembly: An Alternative Strategy for the Construction of Coordination Oligomers and Polymers

Self-assembled oligonuclear and polynuclear complexes have numerous functionalities and potential applications. Generally, such compounds have been constructed by thermal substitution reactions with bridging ligands. Herein, we report bottom-up and photochemical construction of functional coordination oligomers and polymers by photosubstitution-induced self-assembly. The photosubstitution reactions of a ruthenium precursor complex with bridging ligands having pyrazole moieties afford mono-, di-, tri-, tetra-, and pentanuclear ruthenium complexes, Ru₁-Ru₅, which have one-dimensional architectures. Intramolecular hydrogen bonding between each bridging ligand is a key to construct the molecular nanowires. All the complexes have been isolated and thoroughly characterized. The photochemically synthesized ruthenium complexes act as synthons for longer metal-complex-based nanowires with a length of the order of tens-of nanometers. The multinuclear complexes are generated by photoinduced self-assembly in the presence of a base, and they undergo photoinduced disassembly in the presence of acid.