Coordination Networks of a Ditopic Macrocycle Exhibiting Anion-Controlled Dimensional Changes and Crystal-to-Crystal Anion Exchange

다국어 초록 (Multilingual Abstract)

<P>A rationally designed NO<SUB>2</SUB>S<SUB>2</SUB>-donor macrocycle <B>L</B> was synthesized, and anion variation (PF<SUB>6</SUB><SUP>–</SUP>, CF<SUB>3</SUB>CO<SUB>2</SUB><SUP>–</SUP>, NO<SUB>3</SUB><SUP>–</SUP>, and CF<SUB>3</SUB>SO<SUB>3</SUB><SUP>–</SUP>) of its silver(I) complexes was employed as a strategy for controlling their coordination modes and network dimensions. The assembly reactions of <B>L</B> with four silver(I) salts afforded the complexes [Ag<SUB>2</SUB><B>L</B><SUB>2</SUB>](PF<SUB>6</SUB>)<SUB>2</SUB> (<B>1</B>), [Ag<SUB>4</SUB><B>L</B><SUB>2</SUB>(CF<SUB>3</SUB>CO<SUB>2</SUB>)<SUB>4</SUB>]<SUB><I>n</I></SUB> (<B>2</B>), [Ag<SUB>4</SUB><B>L</B><SUB>2</SUB>(NO<SUB>3</SUB>)<SUB>4</SUB>]<SUB><I>n</I></SUB> (<B>3</B>), and {[Ag<SUB>3</SUB><B>L</B><SUB>2</SUB>(CF<SUB>3</SUB>SO<SUB>3</SUB>)<SUB>2</SUB>]CF<SUB>3</SUB>SO<SUB>3</SUB>}<SUB><I>n</I></SUB> (<B>4</B>) that adopt cyclic dimer, 1D, 2D, and pseudo 3D network structures, respectively, with the structure adopted depending on the coordination ability and coordination modes of the anion used. Interestingly, quantitative anion exchange accompanying an irreversible structural conversion from <B>2</B>, <B>3</B>, or <B>4</B> to <B>1</B> was observed in the crystalline state by powder X-ray diffraction (PXRD) and IR spectroscopy. A stepwise mechanistic process from <B>2</B> (CF<SUB>3</SUB>CO<SUB>2</SUB><SUP>–</SUP>, 1D) to <B>3</B> (NO<SUB>3</SUB><SUP>–</SUP>, 2D) by anion exchange was also proposed.</P><P>Depending on the anions (CF<SUB>3</SUB>CO<SUB>2</SUB><SUP>−</SUP> and NO<SUB>3</SUB><SUP>−</SUP>) used in silver(I) complexations with a ditopic macrocycle, 1D and 2D polymeric products were isolated, respectively. The observed anion exchange of CF<SUB>3</SUB>CO<SUB>2</SUB><SUP>−</SUP> in the former with NO<SUB>3</SUB><SUP>−</SUP> is noteworthy because it is undergone quantitatively in the crystalline state, accompanying the dimensional increase from 1D to 2D.</P><P><B>Graphic Abstract</B>
<IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/inocaj/2015/inocaj.2015.54.issue-11/acs.inorgchem.5b00422/production/images/medium/ic-2015-004222_0017.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ic5b00422'>ACS Electronic Supporting Info</A></P>