Amorphization of a Ru- Ru- Cd- Coordination Polymer at Low Pressure

摘要

The water soluble backbone heterometallic polymer {{(PTA)(2) CpRu-m-CN-RuCp(PTA)(2)}-m-CdCl3}(n) (1), which is easily obtained in large amount, was synthesized and its structure determined by single crystal X-ray diffraction. Coordination-polymer 1 becomes amorphous when milled under low pressure (0.5 MPa). The amorphous compound was characterized by MAS-NMR, elemental analysis, TG and Raman spectroscopy. The Raman spectrum of the coordination polymer was assigned by comparison with the Raman spectrum obtained by DFT calculation of a simple model of 1. The analysis of both calculated and experimental Raman spectra showed that Raman spectroscopy can be used to determine if the PTA ligand is mono-or bidentate, giving rise to a method for characterization and future studies of polymeric complexes containing bidentate PTA. The phase transformation of 1 under pressure and temperature was studied by PXR, showing how is possible to model easily this Ru-Ru-Cd inorganic polymer into a variety of different solid forms with possible new properties.