Design of novel copper(II) and zinc(II) coordination polymers based on the 4′-functionalized terpyridines

Add time:08/20/2019    Source:sciencedirect.com

The reaction of 4′-substituted terpyridyl ligand of 4′-hydroxy-2,2′:6′,2″-terpyridine (tpyOH) with zinc(II) acetate resulted in the formation of [Zn(tpyO)(OCOCH3)] (1). Complex 1 forms a one-dimensional polymer via coordination through oxygen atom in which tpyO− acts as a tetra-dentate ligand to afford a highly distorted trigonal bipyramid ZnN3O2. The reaction of zinc(II) acetate with 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine (pytpy) yields the zinc(II) complex [Zn(pytpy)(OCOCH3)(OH)] (2). The penta-coordinated complex [Zn(pytpy)(OCOCH3)](PF6) (3) obtained during the reaction of 2 with NH4PF6, was characterized by X-ray crystallography. The crystal structure of 3 reveals that pytpy acts as a bridging ligand between two metal centers, involved in a highly distorted trigonal bipyramidal geometry ZnN4O to form a 1D directional coordination polymer. The reaction of copper(I) iodide with 4′-(4-tolyl)-2,2′:6′,2″-terpyridine (toltpy) affords the copper(II) complex [Cu(toltpy)I2] (4). Copper(II) acetate was reacted with 4′-substituted terpyridyl ligand of 4′-hydroxy-2,2′:6′,2″-terpyridine (tpyOH) to yield the complex [Cu(tpyOH)(OCOCH3)2] (5). The reaction of copper(II) acetate with 4′-(4-anisyl)-2,2′:6′,2″-terpyridine (atpy) and 4,4′-bipyridine in the presence of NH4PF6 led to the formation of the novel binuclear complex [Cu2(atpy)2(μ-4,4′-bpy)(OCOCH3)2](PF6)2 (6). Crystal structure determination of 6 indicates that there are two crystallographically independent molecules of compound 6 comprise the asymmetric unit. Two copper atoms are further connected by the 4,4′-bipyridine in each form of dinuclear complex, giving rise to a distorted square pyramidal coordination geometry for each of Cu(II) centers. The thermal behaviors of all complexes have been investigated.

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