Abstract
Three new one dimensional ferrocene decorated Hg(ii) based coordination polymers with the general formula of (FcCH(2)N(C2H4OH)NCS2HgX)(n) {X = Cl (FcHgCl); Br (FcHgBr); I (FcHgI)} have been synthesized using a functionalized dithiocarbamate ligand with a redox active ferrocene pendant and -C2H4OH and have been characterized by microanalyses, FTIR, H-1, C-13, and Hg-199 NMR, electronic absorption and photoluminescence spectroscopy. The redox properties of these compounds have been assessed by cyclic voltammtery which suggested their quasi-reversible redox behaviour. Single crystal X-ray diffraction studies suggested that the geometries around all three Hg(ii) polymers are square pyramidal and two such square-pyramids fuse in an antiparallel mode in FcHgCl and FcHgI and in an orthogonal mode in FcHgBr to generate a ferrocene decorated 1D polymeric framework. The adjacent 1D polymeric chains in all three compounds are held by different intermolecular interactions which provide stability to these compounds in the solid state. Also, these compounds exhibit interesting HgMIDLINE HORIZONTAL ELLIPSISX (X = Cl, Br and I) spodium bonding interactions. The nature of all these interactions have been studied by Hirshfeld surface analyses, density functional theory and quantum theory of atoms in molecules (QTAIM). The QTAIM results indicated that HgMIDLINE HORIZONTAL ELLIPSISX interactions are moderately strong with interaction energies of 9.32, 44.37 and 19.56 kJ mol(-1) for chloro, bromo and iodo derivatives, respectively. Further bond order calculations also suggest the presence of spodium bonding interaction in all three polymers.