A Vanadium Porphyrin with Temperature-Dependent Phase Transformation: Synthesis, Crystal Structures, Supramolecular Motifs and Properties

A vanadium porphyrin, V(O)TMcOPP (1; TMcOPP=5, 10, 15, 20-tetrakis(4-methoxyphenyl)-21H, 23H-porphyrin), has been synthesized by solvothermal reactions and characterized by single-crystal X-ray diffractions at room temperature and low temperature to reveal two different structures 1R and 1L, respectively. Both 1R and 1L crystallized in the orthorhombic system, but their space groups were different: Pbca and Pca2(1) for 1R and 1L, respectively. The cell parameters of a, b, and c were different and the cell volume of 1R was larger than that of 1L by circa 200 angstrom(3). 1R and 1L were characteristic of an isolated motif with a five-coordinate vanadium(IV) ion and a saddle-distorted nonplanar porphyrin macrocycle. Molecules of 1R were interconnected through hydrogen-bonding interactions to yield a 3D framework; whilst for the low-temperature phase 1L, there were more hydrogen-bonding interactions that link the molecules to construct a more-complex 3D supramolecular network. In a solution of acetone, the title compound exhibited purple and green colors at room temperature and low temperature, respectively, which is unprecedented for vanadium porphyrins. The spectral data of UV/Vis, FT-IR, and MALDI-TOF-MS of 1R and 1L are reported together with the electrochemical data.