• Bulletin of the Korean Chemical Society
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• v.27 no.5
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• pp.713-717
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• 2006

$S_2O$-donor macrocyclic isomers incorporating a xylyl group in o- ($L^1$), m- ($L^2$) and p-positions ($L^3$) extract no metal ions except silver(I) from aqueous to chloroform phase. And the magnitudes of %Ex for silver(I) are in the order of $L^1$ > $L^2$ > $L^3$. Taking this result into account, $L^1$-$L^3$ were utilized as membrane active components to prepare potentiometric silver(I)-selective electrodes. The proposed macrocycles-based electrodes E1 ($L^1$), E2 ($L^2$) and E3 ($L^3$) exhibited comparable results which show considerable selectivity toward silver(I) over alkali, alkali earth and other transition metal ions. Comparative NMR study on $L^1$-$L^3$ and their complexes with silver(I) in solution was also accomplished. In addition, a unique sandwich-type complex $[Ag(L^1)_2]CIO_4$ was prepared from the assembly reaction of $L^1$ with $AgClO_4$ and structurally characterized by an X-ray diffraction analysis.

• Bulletin of the Korean Chemical Society
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• v.34 no.3
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• pp.725-730
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• 2013

An investigation of the coordination behavior of sulfur-containing mixed-donor tribenzo-macrocycles $L^1-L^3$ ($L^1$: 20-membered $O_3S_2$, $L^2$: 20-membered $O_2S_3$, and $L^3$: 23-membered $O_4S_2$) with $d^{10}$-metal ($Ag^+$, $Hg^{2+}$, and $Pb^{2+}$) salts is reported. The X-ray structures of five complexes (1-5) with different structural types and stoichiometries, including mono- to dinuclear species have been determined. Reactions of $L^2$ and $L^3$ with the silver(I) salts ($PF_6{^-}$ and $SCN^-$) afforded two dinuclear 2:2 (metal-to-ligand) complexes with different arrangements: a sandwich-type cyclic dinuclear complex $[Ag_2(L^2)_2](PF_6)_2{\cdot}3CH_2Cl_2$ (1) and a linear dinuclear complex $[Ag_2(L^3)_2(SCN)_2]$ (2), in which two monosilver(I) complex units are linked by an Ag-Ag contact. Reactions of $L^1$ and $L^2$ with mercury(II) salts ($SCN^-$ and $Cl^-$) gave a mononuclear 1:1 complexes $[Hg(L^1)(SCN)_2]$ (3) and $[Hg(L^2)Cl_2]$ (4) with anion coordination in both cases. $L^2$ reacts with lead(II) perchlorate to yield a mononuclear sandwich-type complex $[Pb(L^2)_2(ClO_4)_2]$ (5), giving an overall metal coordination geometry of eight with a square antiprism arrangement. From these results, the effects of the donor variation and the anioncoordination ability on the resulting topologies of the soft metal complexes are discussed.