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Open AccessArticle

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

Department of Chemistry, University Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland
Author to whom correspondence should be addressed.
Crystals 2018, 8(12), 461;
Received: 28 November 2018 / Revised: 7 December 2018 / Accepted: 7 December 2018 / Published: 10 December 2018
(This article belongs to the Special Issue Metal Phosphonates and Phosphinates)
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. View Full-Text
Keywords: phosphonate ester; zinc(II); 2,2′:6′,2″-terpyridine; crystal structure phosphonate ester; zinc(II); 2,2′:6′,2″-terpyridine; crystal structure
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MDPI and ACS Style

Zare, D.; Prescimone, A.; Constable, E.C.; Housecroft, C.E. Where Are the tpy Embraces in [Zn{4′-(EtO)2OPC6H4tpy}2][CF3SO3]2? Crystals 2018, 8, 461.

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