Syntheses, crystal structures, luminescent and magnetic properties of two molecular solids containing naphthylmethylene triphenylphosphinium cations and tetra(isothiocyanate)cobalt(II) dianion

The reaction of CoCl2 with the naphthalene methylated triphenylphosphinium bromide [n-NAPMeTPP]Br (n = 1, 2) and KSCN, in a methanolic medium at ambient temperature, leads to the self-assembly formation of hybrid 2:1 organic-inorganic molecular solids, [1-NAPMeTPP](2)[Co(NCS)(4)](1) and [2-NAPMeTPP](2)[Co(NCS)(4)](2) ([NAPMeTPP](+) = (naphthylmethylene)(triphenyl)phosphinium), which have been characterized by elemental analyses, IR spectroscopy, UV-Vis spectra, ESI-MS, molar conductivity and single-crystal X-ray diffraction structural analyses. Compound 1 crystallizes in the orthorhombic space group Pna2(1), while 2 does in the monoclinic space group C2/c. The cations form a dimer through the weak intermolecular C-H...pi it interactions in 1 and it pi...pi interaction in 2, while the anion and cation are linked by the C-H...S hydrogen bond in 1. Two molecular solids show dual functionalities: (1) the broad fluorescence emission around 400 nm in the solid state at room temperature; (2) the weak antiferromagnetic coupling behavior. (C) 2015 Elsevier B.V. All rights reserved.