title: Electron transfer vs coordination chemistry: isomer-specific binding of HgII by an ortho-Wurster's thiacrown ether.
abstract: Isomeric p- and o-phenylenediamine-containing macrocyclic hosts (Wurster's thiacrown ethers L1 and L2, respectively) were prepared and studied as Hg(II) ionophores. The distinct electrochemical properties of the two hosts allowed for the formation of a coordination compound with the ortho-Wurster's thiacrown ether but not the para isomer. In the latter case, the Hg(II) ion served as an oxidant in an electron-transfer reaction with the host. Solutions of the Hg(II) complex of L2 were studied by 13C NMR spectroscopy and cyclic voltammetry and revealed a strong interaction between the redox-active phenylenediamine subunit and the bound metal cation. An X-ray analysis confirmed the participation of the three macrocyclic S atoms and both phenylenediamine N atoms in the stabilization of the complex.
authors.affiliation: Department of Chemistry, University of Texas at Dallas, Richardson, TX 75083, USA. sibertj@utdallas.edu
authors.forename: John W
authors.initials: JW
authors.lastname: Sibert
authors.forename: Philip B
authors.initials: PB
authors.lastname: Forshee
authors.forename: Vincent
authors.initials: V
authors.lastname: Lynch