Abstract

Second-sphere coordination refers to any intermolecular interactions with the ligands directly bound to the primary coordination sphere of a metal ion. Four supramolecular complexes, 0.5[L·2H]2+·0.5[MCl4]2−·[CH3OH]·0.5[CH2Cl2] (M = Co, crystal 1; M = Mn, crystal 2), 0.5[L·2H]2+·0.5[ZnBr4]2−·[CH3OH]·0.5[CH2Cl2] (crystal 3), and 0.5[L·2H]2+·0.5[Cu2Br4]2−·H2O (crystal 4), based on naphthalene-based ligand N,N,N′,N′-tetra-p-methylnaphthyl-ethanediamine (L), have been synthesized. X-ray analysis reveals that 1–3 are isostructural, in which the methanol molecules are bridges, connecting the protonated L and metal chloride anions via N–H⋯O and O–H⋯Cl (Br) interactions to construct the host framework, and forming X-shaped cavity accessible for the inclusion of weakly polar guest molecules of dichloromethane. Dichloromethane is connected with the host framework through van der Waals forces. In 4, a dinuclear anion [Cu2Br4]2− is connected with the ligand through N–H⋯Br interactions, in which the water molecules are accommodated between chains formed by the ligand and [Cu2Br4]2−. Structure stability, thermal analysis, and photoluminescent properties were studied for 1–4.

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