Binding of Mono- and Dianions Within Silver Thiazolylurea Tweezers and Capsules

Document Type

Article

Publication Date

10-16-2017

Department

Chemistry and Biochemistry

School

Mathematics and Natural Sciences

Abstract

A silver thiazolylurea complex, [Ag(TUTh)2]+, has been used as a host species for geometrically differently shaped mono- and dianions: trigonal planar (NO3–), tetrahedral (SO42–), and octahedral (SiF62–). In the presence of nitrate a 1:1 near-planar tweezer host–guest species is formed, with poor binding in solution despite excellent geometric complementarity being found between the host and the anion in the solid state. In the presence of either SO42– or SiF62– a 2:1 host–guest species is formed, whereby the guest is held in a capsulelike arrangement stabilized by an array of eight NH hydrogen-bond donors, as confirmed by X-ray crystallographic studies. Solution studies in DMSO-d6 support the host–guest stoichiometry seen in the solid state. The binding constant between SO42– and [Ag(TUTh)2]+ was calculated to be K21 = 2511 M–2 and was shown to be the dominant species in solution, in excellent agreement with the solid-state studies. However, upon the addition of SiF62– ions different speciation is observed: H2·G (capsule), H·G (tweezer), and H·G2 during the course of the study.

Publication Title

Inorganic Chemistry

Volume

56

Issue

20

First Page

12535

Last Page

12541

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