Structural, spectral and magnetic studies of two Co(II)-N-heterocyclic diphosphonates based on multinuclear units

Abstract

Two examples of Co(II)-N-heterocyclic coordination polymers based on 1-hydroxyethylidenediphosphonic acid (H5L=CH3C(OH)(PO3H2)2), namely 0.5(H3NCH2CH2NH3)·[Co6(Cl2)(H3L)2(H2L)(HL)(2,2′-bipy)6] 1 and 2(NH4)·[Co3(HL)2(H2O)2(phen)2]·2(H2O) 2, have been solvothermally obtained by introducing the second ligands 2,2′-bipyridine/1,10-phenanthroline (2,2′-bipy/phen) and characterized by powder X-ray diffraction (PXRD), elemental analysis, IR, TG-DSC. The single-crystal X-ray diffractions show that compound 1 possesses a 0-D structure with hexa-nuclear cluster [Co6(O–P–O)8] built through single/double O–P–O bridges and compound 2 displays a 1-D ladder-like chain structure with magnetic topology building blocks [Co4(O–P–O)4]n. Then H-bonding and π–π stacking interactions further expand the two low-dimensional structures into three-dimensional supramolecular frameworks. Fluorescent measurements reveal that both the maximum emission peaks of 1–2 are centered at 423nm, mainly deriving from intraligand π*–π transition state of N-heterocyclic ligand 2,2′-bipy/phen, respectively. Magnetism data indicate that 1 exhibits antiferromagnetic behavior within hexa-nuclear Co(II) clusters, while 2 shows weak ferromagnetic interactions in 1-D topology Co(II)-chain, showing promising potential as magnetic materials.