Paddlewheel‐Type Dirhodium Tetrapivalate Based Coordination Polymer: Synthesis, Characterization, and Self‐Assembly and Disassembly Transformation Properties

Abstract

An extended one‐dimensional chain‐type coordination polymer, [Rh 2 (piv) 4 (tpy)] n ( 1 ; piv = pivalate, tpy = 2,2′:6′,2′′‐terpyridine), has been synthesized and characterized by single‐crystal and powder X‐ray diffraction analyses, elemental analysis, IR spectrosopy, thermogravimetric analysis, UV/Vis diffuse reflectance spectroscopy, and magnetic measurements at 300 K. This complex shows unique repeatable self‐assembly and disassembly transformation properties. Polymer 1 readily decomposed to its constituent building blocks, that is, [Rh 2 (piv) 4 ] and tpy, in organic solvents at 300 K, but the disassembly product of 1 readily re‐self‐assembled to give 1 as a crystalline product in aqueous ethanol solution at 373 K. In addition, 1 was obtained as a crystalline powder by a water‐assisted mechanochemical synthesis route.