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Article
Metal Substitution and Solvomorphism in Alkylthiolate-Bridged Zn-3 and HgZn2 Metal Clusters
ACS OMEGA
  • Madeline R Hallinger, College of William and Mary
  • Alison C Gerhard, College of William and Mary
  • Mikhaila D Ritz, College of William and Mary
  • Joshua S Sacks, College of William and Mary
  • John C Poutsma, College of William and Mary
  • Robert D Pike, College of William and Mary
  • Deborah C Bebout, College of William and Mary
Document Type
Article
Publication Date
10-1-2017
Disciplines
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-pyridyl-methyl)-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.

DOI
10.1021/acsomega.7b01087
Citation Information
Madeline R Hallinger, Alison C Gerhard, Mikhaila D Ritz, Joshua S Sacks, et al.. "Metal Substitution and Solvomorphism in Alkylthiolate-Bridged Zn-3 and HgZn2 Metal Clusters" ACS OMEGA Vol. 2 Iss. 10 (2017)
Available at: http://works.bepress.com/robert-pike/152/