초록
<P>Self-assembly of M(ClO<SUB>4</SUB>)<SUB>2</SUB> (M<SUP>2+</SUP> = Ni<SUP>2+</SUP>, Cu<SUP>2+</SUP>, and Zn<SUP>2+</SUP>) with (1<I>S</I>,1′<I>S</I>,1′′<I>S</I>,2<I>R</I>,2′<I>R</I>,2′′<I>R</I>)-(benzenetricarbonyltris(azanediyl))tris(2,3-dihydro-1<I>H</I>-indene-2,1-diyl) trinicotinate (<I>s</I>,<I>r</I>-L) and the corresponding enantiomer (<I>r</I>,<I>s</I>-L) as a pair of chiral tridentate donors gives rise to the chiral cage pairs [M<SUB>3</SUB>(<I>s</I>,<I>r</I>- and <I>r</I>,<I>s</I>-L)<SUB>2</SUB>](ClO<SUB>4</SUB>)<SUB>6</SUB>. For the two pairs of [(Me<SUB>2</SUB>CO)(H<SUB>2</SUB>O)@M<SUB>3</SUB>(<I>r</I>,-<I>s</I> and <I>s</I>,<I>r</I>-L)<SUB>2</SUB>](ClO<SUB>4</SUB>)<SUB>6</SUB> (M<SUP>2+</SUP> = Ni<SUP>2+</SUP> and Zn<SUP>2+</SUP>), the inner cavity is occupied by both an acetone and a single water molecule, whereas for the copper(<SMALL>II</SMALL>) pair of [Me<SUB>2</SUB>CO@Cu<SUB>3</SUB>(<I>r</I>,<I>s</I>- and <I>s</I>,<I>r</I>-L)<SUB>2</SUB>](ClO<SUB>4</SUB>)<SUB>6</SUB> under the same conditions, the cavity is filled by only one acetone molecule. Thus, the encapsulation of guest molecules into the cages during self-assembly shows significant metal(<SMALL>II</SMALL>) ion effects. These chiral cages are effective for the enantio-recognition of chiral (<I>S</I>)-2-butanol and (<I>R</I>)-2-butanol <I>via</I> the shifts of the electrochemical oxidation potentials obtained by the linear sweep voltammetry (LSV) technique, density functional theory (DFT) calculations, and the chiral 2-butanol adsorption in the single-crystal-to-single-crystal (SCSC) mode.</P><P>Graphic Abstract</P><P>The chiral cage pairs [M<SUB>3</SUB>(<I>s</I>,<I>r</I>- and <I>r</I>,<I>s</I>-L)<SUB>2</SUB>] (M<SUP>2+</SUP> = Ni<SUP>2+</SUP>, Cu<SUP>2+</SUP>, and Zn<SUP>2+</SUP>) show a significant Jahn-Teller distortion effect. These chiral cages are effective for the enantio-recognition of chiral (<I>S</I>)-2-butanol and (<I>R</I>)-2-butanol using electrochemistry.<BR/><IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=d4dt01198h'/><BR/></P>