Mononickel(II), dimercury(II), and 1-D polymeric silver(I) complexes with a ditopic 18-membered N₂O₂S₂-macrocycle

다국어 초록 (Multilingual Abstract)

<P><B>Abstract</B></P> <P>A ditopic 18-membered N<SUB>2</SUB>O<SUB>2</SUB>S<SUB>2</SUB>-macrocycle (<B>L</B>) incorporating hard (NO<SUB>2</SUB>) and soft (NS<SUB>2</SUB>) binding sites in each side was employed and its three complexes (<B>1</B>–<B>3</B>) exhibiting different stoichiometries, geometries, and topologies have been prepared and structurally characterized. First, nickel(II) nitrate hexahydrate reacts with <B>L</B> to give a mononuclear complex [Ni(<B>L</B>)](NO<SUB>3</SUB>)<SUB>2</SUB>·2H<SUB>2</SUB>O (<B>1</B>) in which the metal center locates inside the macrocyclic cavity adopting a hexa-coordinated octahedral geometry shielded by the strongly bound macrocycle from the anion and solvent. While, silver(I) tetrafluoroborate afforded a one-dimensional coordination polymer {[Ag(<B>L</B>)]BF<SUB>4</SUB>}<SUB> <I>n</I> </SUB> (<B>2</B>) with an <B>L</B>-Ag-<B>L</B>-Ag pattern. In <B>2</B>, the silver(I) center is penta-coordinate with NO donors from one <B>L</B> and NS<SUB>2</SUB> donors from an adjacent <B>L</B> to form a sandwich-type adopting a distorted trigonal bipyramidal geometry. Mercury(II) chloride yielded a dinuclear complex [Hg<SUB>2</SUB>(<B>L</B>)Cl<SUB>4</SUB>] (<B>3</B>) in which two mercury(II) ions locate opposite side of <B>L</B> in a chair form. Each mercury(II) center in <B>3</B> is penta-coordinate, being bound to one pyridine N atom, two O(S) donors in the compositional disorder, and two chloride ions adopting a distorted square-pyramidal geometry. The comparative NMR studies show the preferential binding affinity of silver(I) over potassium(I) toward <B>L</B>.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Three supramolecular complexes of a ditopic macrocycle including a 1-D silver(I) coordination polymer have been prepared and structurally characterized. </LI> <LI> Silver(I) tetrafluoroborate afforded a one-dimensional coordination polymer with an <B>L</B>-Ag-<B>L</B>-Ag pattern. </LI> <LI> The NMR studies of the ditopic macrocycle show the preferential binding affinity of silver(I) over potassium(I). </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>A ditopic 18-membered N<SUB>2</SUB>O<SUB>2</SUB>S<SUB>2</SUB>-macrocycle incorporating hard and soft binding sites was employed and its three complexes including a 1-D polymeric silver(I) complex have been prepared and structurally characterized.</P> <P>[DISPLAY OMISSION]</P>