A redox active rod coordination polymer from tetrakis(4-carboxylic acid biphenyl)tetrathiafulvalene

An enlarged version of the ubiquitous tetrathiafulvalene-tetrabenzoic acid is described, with 4,4 '-biphenyl moieties as spacers between the coordination moieties and the electroactive core. The obtained rectangular ligand has a 14 x 22 angstrom 2 size and is combined with Zn(ii) under solvothermal conditions to yield a coordination polymer endowed with large cavities of ca. 15 x 11 angstrom 2/10 x 10 angstrom 2. The topology of the material is discussed in detail using the Points of Extension and Metals (PE&M) or the Straight-rod (STR) representation, and the sqc1121 or tfo topological type of the structure is observed, respectively. Its stability towards solvent removal and electrical properties are discussed. The material does not present any permanent porosity upon desolvation according to nitrogen sorption measurements at 77 K. Nevertheless, a significant increase in conductivity is observed on compressed pellets of the material upon post-synthetic oxidation with iodine. Raman spectroscopy combined with density functional theory (DFT) calculations has been used to characterize the oxidation state of tetrakis(4-carboxylic acid biphenyl)tetrathiafulvalene for coordination polymers. A sprawling scaffold. Tetrathiafulvalene-tetrabenzoic acid has been widely used in redox active porous coordination polymers. Herein is reported the extension of the spacers between the redox active core and the SBUs, and the related PCP structure.