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Anion-controlled circular dichroism spectral changes in Hg2+ complexes with a chiral bidentate ligand
Mari Ikeda1, Shunsuke Kuwahara, Shim Sung Lee
1Department of Chemistry, Faculty of Science, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan.
Abstract:
Anion-controlled circular dichroism (CD) spectral changes in Hg(2+) complexes with a chiral bidentate ligand are reported. Although the Hg(CF(3)SO(3))(2) and Hg(CF(3)CO(2))(2) complexes with (R)-(-)-1-(naphthalen-1-yl)-N,N-bis(pyridin-4-ylmethyl)ethanamine, (R)-(-)-1, show significant CD spectral changes, no CD spectral changes were observed in the HgCl(2), HgBr(2), Hg(CN)(2), or Hg(CH(3)CO(2))(2) complexes. X-ray analysis indicates that both the (R)-(-)-1-Hg(CF(3)SO(3))(2) and (R)-(-)-1-HgCl(2) complexes form a coordination polymer and a discrete 2:3 [=(R)-(-)-1/HgCl(2)] complex with a figure-eight structure. X-ray crystallography revealed that (i) the Hg-Hg distances bridged by anions vary depending on the anions used and (ii) a coordination polymer cannot be formed when the Hg-Hg distances are too short. Therefore, the formation of a coordination polymer is required to give the observed significant CD spectral changes.
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