Abstract
A novel heteroleptic paddlewheel-type dirhodium (Rh2) complex [Rh2(O2CCH3)3(PABC)] (1; PABC = para-aminobenzenecarboxylate), which has an amino group as a potential donor site for coordination with the metal ion, was synthesized and characterized by 1H NMR, ESI-TOF-MS, infrared spectra, and elemental analysis. The slow evaporation of N,N-dimethylformamide (DMF)-dissolved 1 produces the purple-colored crystalline polymeric species [Rh2(O2CCH3)3 (PABC)(DMF)]n (1P). Single-crystal and powder X-ray diffraction analyses, as well as thermo-gravimetric analysis, clarified that 1P formed a one-dimensional polymeric structure, in which the two axial sites of the Rh2 ion in 1P are coordinated by a DMF molecule and an amino group of the PABC ligand of the neighboring molecule 1, by coordination-induced self-assembly (polymerization) with an Rh-amino bond. The reversible structural change (self-assembly and disassembly transformations) between the discrete species [Rh2(O2CCH3)3(PABC)(DMF)2] (1D; green solution) and the polymeric species 1P (purple solid) was accompanied by a color change, which easily occurred by the dissolution and evaporation procedures with DMF.
Highlights
We successfully developed a new synthetic strategy for coordination polymers (CPs) with heteroleptic paddlewheel-type Rh2 -secondary building units (SBUs) using coordination-induced self-assembly with an amino group of the paddlewheel‐type Rh2‐SBUs using coordination‐induced self‐assembly with an amino group of the PABC ligand
Single‐crystal X‐ray diffraction analyses clarified that 1P, which is obtained by the evaporation of DMF-dissolved 1, forms a one-dimensional polymeric structure in which two axial sites slow evaporation of DMF‐dissolved 1, forms a one‐dimensional polymeric structure in which two of the Rh ion in 1P are coordinated by a DMF molecule and an amino group of the PABC ligand of the axial sites2of the Rh2 ion in 1P are coordinated by a DMF molecule and an amino group of the PABC
It is confirmed that polymeric species 1P can be re-dissolved in ligand of the neighboring molecule 1
Summary
Paddlewheel-type dirhodium (Rh2 ) complexes have been attracting considerable interest owing to the basic understanding of their molecular geometries and electronic structures with metal-metal bonds [1] as well as their intriguing properties as antitumor agents [2,3,4], chemical sensors [5,6,7], and catalysts for various types of organic reactions [8,9,10,11] and photochemical and electrochemical hydrogen evolution from aqueous solutions [12,13,14]. A considerable number of experimental and theoretical studies have adequately evaluated the synthesis, molecular geometries, and electronic structures of homoleptic Rh2 complexes with the same bridging carboxylate ligands, [Rh2 (O2 CR) L2 ]. The first two conventional synthetic strategies for the production of Rh2carboxylate
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