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In this paper, the bromo- and phosphonate-ester-functionalized complexes [Zn(1)2][CF3SO3]2 and [Zn(2)2][CF3SO3]2 (1 = 4′-(4-bromophenyl)-2,2′:6′,2″-terpyridine, 2 = diethyl (4-([2,2′:6′,2″-terpyridin]-4′-yl)phenyl)phosphonate) are reported. The complexes have been characterized by electrospray mass spectrometry, IR and absorption spectroscopies, and multinuclear NMR spectroscopy. The single-crystal structures of [Zn(1)2][CF3SO3]2.MeCN.1/2Et2O and [Zn(2)2][CF3SO3]2 have been determined and they confirm {Zn(tpy)2}2+ cores (tpy = 2,2′:6′,2″-terpyridine). Ongoing from X = Br to P(O)(OEt)2, the {Zn(4′-XC6H4tpy)2}2+ unit exhibits significant “bowing” of the backbone, which is associated with changes in packing interactions. The [Zn(1)2]2+ cations engage in head-to-tail 4′-Phtpy...4′-Phtpy embraces with efficient pyridine...phenylene π-stacking interactions. The [Zn(2)2]2+ cations pack with one of the two ligands involved in pyridine...pyridine π-stacking; steric hindrance between one C6H4PO(OEt)2 group and an adjacent pair of π-stacked pyridine rings results in distortion of backbone of the ligand. This report is the first crystallographic determination of a salt of a homoleptic [M{4′-(RO)2OPC6H4tpy}2]n+ cation.

Where Are the tpy Embraces in [Zn{4′-(EtO)2OPC6H4tpy}2][CF3SO3]2?