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Issue 8, 2013
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Effects of structures of HgX2 complexes (X = CF3SO3 and Cl) with chiral bidentate ligands on circular dichroism spectra

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Abstract

The effects of the structures of HgX2 complexes (X = CF3SO3 and Cl) with chiral bidentate ligands [(R)-(−)-1-(1-naphthyl)-N,N-bis(pyridin-4-ylmethyl)ethanamine, (R)-(+)-1-phenyl-N,N-bis(pyridin-4-ylmethyl)ethanamine, (R)-(−)-1-(1-naphthyl)-N,N-bis(pyridin-3-ylmethyl)ethanamine, and (R)-(+)-1-phenyl-N,N-bis(pyridin-4-ylmethyl)ethanamine] on circular dichroism (CD) spectra are reported. The CD spectra of free (R)-(−)-1a and (R)-(+)-1b, which have 4-pyridyl groups, are similar to those of (R)-(−)-2a and (R)-(+)-2b, which have 3-pyridyl groups. When equimolar amounts of Hg(CF3SO3)2 are added to these ligands, a decrease in the CD intensity of (R)-(−)-2a is observed, and significant spectral changes (intensity and shape) are observed in (R)-(−)-1a, (R)-(+)-1b, and (R)-(+)-2b. X-ray crystal structures suggest that the (R)-(−)-2a/Hg(CF3SO3)2 complex is a coordination polymer with no bridging CF3SO3 anions, whereas the (R)-(−)-1a/Hg(CF3SO3)2 and (R)-(+)-1b/Hg(CF3SO3)2 complexes are coordination polymers with CF3SO3 anion bridges, and the (R)-(+)-2b/Hg(CF3SO3)2 complex has a tricyclic structure bridged by CF3SO3 anions. Two different conformers, which have clockwise and counter-clockwise screw senses between the naphthalene axis and the pyridine axis, are observed in the ligand components of the (R)-(−)-2a/Hg(CF3SO3)2 complex. In contrast, the X-ray structures of the (R)-(−)-2a/HgCl2 and (R)-(+)-2b/HgCl2 complexes are one-dimensional coordination polymers without bridging Cl anions. The significant CD spectral changes in the HgX2 complexes with different chiral bidentate ligands require formation of rigid structures and a single-directional screw sense between chromophores.

Graphical abstract: Effects of structures of HgX2 complexes (X = CF3SO3 and Cl) with chiral bidentate ligands on circular dichroism spectra

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Publication details

The article was received on 13 Nov 2012, accepted on 04 Dec 2012, published on 04 Dec 2012 and first published online on 04 Dec 2012


Article type: Paper
DOI: 10.1039/C2DT32712K
Citation: Dalton Trans., 2013,42, 3009-3014
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    Effects of structures of HgX2 complexes (X = CF3SO3 and Cl) with chiral bidentate ligands on circular dichroism spectra

    M. Ikeda, S. Kuwahara, S. S. Lee and Y. Habata, Dalton Trans., 2013, 42, 3009
    DOI: 10.1039/C2DT32712K

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