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Metal Substitution and Solvomorphism in Alkylthiolate-Bridged Zn3 and HgZn2 Metal Clusters
Hallinger, Madeline R. Gerhard, Alison C. Ritz, Mikhaila D. Poutsma, John C. Pike, Robert D.
Hallinger, Madeline R.
Gerhard, Alison C.
Ritz, Mikhaila D.
Poutsma, John C.
Pike, Robert D.
Abstract
The impact of substituting Hg(II) for Zn(II) in a thiolate-bridged trinuclear cluster with parallels to a metallothionein metal cluster was investigated. A new solvomorph of [Zn(ZnL)2](ClO4)2 (1) (L = N-(2-pyridylmethyl)-N-(2-(ethylthiolato)-amine) and five solvomorphs of a new compound [Hg(ZnL)2](ClO4)2 (2) were characterized by single-crystal X-ray crystallography. The interplay of hydrogen bonding and aromatic-packing interactions in producing lamellar, 2D lamellar, and columnar arrangements of complex cations in the crystalline state is discussed. Both variable temperature proton nuclear magnetic resonance and electrospray ion-mass spectrometry (ESI-MS) suggest that the complex ions of 1 and 2 are the predominant solution species at moderate concentrations. ESI-MS was also used to monitor differences in metal ion redistribution as 1 was titrated with Hg(ClO4)2 and [HgL(ClO4)]. These studies document the facile replacement of Zn(II) by Hg(II) with the preservation of the overall structure in thiolate-rich clusters.
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2017-10-01
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Chemistry
DOI
https://doi.org/10.1021/acsomega.7b01087