Supramolecular frameworks composed of copper(II), zinc(II), and ferrous(II) complexes having 3-bromo or 3,8-dibromo-1,10-phenanthroline ligand with different molar ratios of metal and ligand

Abstract

Three copper(II), one zinc(II), and one ferrous(II) complexes having 3-bromo or 3,8-dibromo-1,10-phenanthroline ligand with different metal/ligand molar ratios, formulated as [Cu(3-bromo-phen)(ClO4)(C3H7NO)2(H2O)](ClO4) (1), [Cu(3,8-dibromo-phen)(ClO4)(C3H7NO)2(H2O)](ClO4) (2), [Cu(3,8-dibromo-phen)(ClO4)(H2O)3](ClO4)(H2O)3 (3), [Zn(3,8-dibromo-phen)2(H2O)2](ClO4)2(H2O)2 (4), and [Fe(3,8-dibromo-phen)3](ClO4)2(H2O)(CH4O)(C3H6O)2 (5) (phen = 1,10-phenanthroline), have been synthesized and characterized in this paper. X-ray single-crystal diffraction studies reveal the different crystallographic symmetry and packing fashions between neighboring phen rings in 1:1 Cu(II) complexes 1–3 due to the alteration of bromo substituent 1,10-phenanthroline ligands and coordinated or free solvent molecules. Additionally, in 1:2 Zn(II) and 1:3 Fe(II) complexes 4 and 5, continuous π–π stacking and alternating π–π and dimeric p–π stacking are found. Five mononuclear complexes having 3-bromo or 3,8-dibromo-1,10-phenanthroline ligand with different molar ratios of metal and ligand have been spectrally and structurally characterized, where different one-dimensional π–π stacking modes are found in the crystal packing of 1, 3, 4, and 5.