A novel one-dimensional chain built of vanadyl ions and pyrazine-2,5-dicarboxylate.

We present a new coordination polymer, {[VO(pzdc)(H2O)2] H2O}n, built from vanadyl and pyrazine-2,5-dicarboxylate (pzdc) ions. It consists of a one-dimensional chain of vanadyl ions linked by pzdc ions. The carboxylate groups show monodentate coordination, while the pyrazine ring is present both in non-coordinated and coordinated modes. This novel structure is stabilized by an intricate network of hydrogen bonds. The material is highly robust, and thermally stable up to 400 K. It is also antiferromagnetic, with a maximum magnetic susceptibility at ca. 50 K. The orbital shape and population analysis by means of DFT analysis confirm the π-acceptor role of the aromatic nitrogen function of the ligand, while the oxygen-based moieties (carboxylates from pzdc, the aqua ligands and oxo from V=O group) behave as normal donors. Charting the density flow related with significant transitions computed by time-dependent DFT, we determined the ligand-to-metal charge transfer processes. The topology of the chain complex implies two different types of connecting bridges. Using Broken Symmetry DFT modelling gives evidence for two different exchange coupling mechanisms between the vanadyl ions along each of these two molecular bridges. One is strongly antiferromagnetic, practically reducing the chain to 'vanadyl dimers'. The other is almost uncoupled, due to the large distance between the vanadyl ions.