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

• Two molecular solids containing [Co(NCS)4]2− dianion were prepared and characterized.
• The cations form a dimer through the weak intermolecular C–H⋯π or π⋯π interactions.
• Two molecular solids show dual functionalities: fluorescence and antiferromagnetic behavior.

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 Pna21, while 2 does in the monoclinic space group C2/c. The cations form a dimer through the weak intermolecular C–H⋯π interactions in 1 and π⋯π 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.

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