Asymmetric twisting and chirality probing properties of quadruple-stranded helicates: coordination versatility and chirality response of Na(+), Ca(2+), and La(3+) complexes with octadentate cyclen ligand

Inorganic Chemistry
Hitomi MisakiHiroshi Tsukube

Abstract

A series of Na(+), Ca(2+), and La(3+) complexes with octadentate cyclen ligand were prepared and structurally characterized in the crystal and solution states. The employed cyclen ligand formed 6-, 7-, and 9-coordinated, crystalline complexes with Na(+), Ca(2+), and La(3+) cations, respectively, in which the parent cyclen ring and quinoline-functionalized side arms were cooperatively coordinated. These three metal cations provided the quadruple-stranded helicates in CH(3)CN-C(2)H(5)OH solutions. In each helicate, four quinoline-functionalized side arms were arranged in a propeller-like fashion to yield an enantiomer-pair of Delta- and Lambda- forms. Addition of a chiral anion to the cyclen-Ca(2+) complex solution induced circular dichroism (CD) signals around the quinoline chromophore, which indicated that 1:1 diastereomeric complexation between the Ca(2+) complex and the chiral anion imposed the stereoisomeric equilibrium. The intensity and sign of the observed CD signal were significantly dependent on both the absolute configuration and the enantiomeric purity of the added anion. The corresponding cyclen-Na(+) complex rarely induced a CD signal, while the La(3+) complex exhibited complicated anion-induced spectral changes. Th...Continue Reading

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Citations

Aug 10, 2012·Inorganic Chemistry·Claire DevilleAlan F Williams
Jun 3, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Nathalie BaradelMarc Henry
Oct 5, 2012·Chemical Society Reviews·Satoshi Shinoda
Nov 15, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Yuji MikataHideo Konno
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Jul 10, 2012·Chemical Society Reviews·Katsuhiko ArigaHiroshi Tsukube
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Apr 25, 2014·Chemical Communications : Chem Comm·Matthew EverettGillian Reid
Sep 22, 2012·Chemical Communications : Chem Comm·Hiroshi ItoSatoshi Shinoda
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Aug 29, 2020·Inorganic Chemistry·Eunji LeeYoichi Habata
May 19, 2018·The Journal of Organic Chemistry·Aleksandra GerusJerzy Lisowski

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