Abstract
By introducing the second organic N-heterocyclic ligands 2,2′-bipyridine (2,2′-bipy)/1,10-phenanthroline (phen), two mono-/bi-nuclear examples of Cu(II)-diphosphonate coordination polymers based on 1-hydroxyethylidenediphosphonic acid (H5L=CH3C(OH)(PO3H2)2), [Cu(H4L)2(2,2′-bipy)]·H2O 1 and [Cu(H3L)(phen)]2·(HOCH2CH2OH)0.52, have been solvothermally obtained and characterized by powder X-ray diffraction, elemental analysis, IR, TG–DSC. The single-crystal X-ray diffractions show that both the two compounds possess zero-dimensional structures, built from mononuclear unit [CuO4N2]n for 1 and binuclear unit [–Cu–O–P–O–]2n with a double O–P–O bridge for 2 in syn-anti fashion. Then H-bond or/and π–π interactions further expand the two zero-dimensional structures into the three-dimensional supramolecular frameworks. Fluorescent measurements reveal that the maximum emission peaks of 1–2 centered at 433.5nm for 1 and 434.5nm for 2, respectively, are mainly caused by intraligand π*–π emission state of N-heterocyclic ligands (λex=235nm). The further magnetic study shows the two coordination polymers exhibit antiferromagnetic behavior for 1 between the mononuclear units, while ferromagnetic behavior for 2 derived from double O–P–O bridges in syn-anti mode between the metal centers.
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