Metal binding characteristics of a laterally nonsymmetric aza cryptand upon functionalization with a π-acceptor group

The laterally nonsymmetric aza cryptand synthesized by condensing tris(2-aminoethyl)amine (tren) with trist{[2-(3(oxomethyl)phenyl)oxy]ethyllamine readily forms mononuclear inclusion complexes with both transition and maingroup metal ions. In these complexes, the metal ion occupies the tren-end of the cavity making bonds with the three secondary amino and the bridgehead N atoms. When a strong pi-acceptor group such as 2,4-dinitrobenzene is attached to one of the secondary amines, the binding property of the cryptand changes drastically. When perchlorate or tetrafluoroborate salts of Ni(II), Cu(II), Zn(II), or Cd(II) are used, the metal ion enters the cavity which can be monitored by the hypsochromic shift of the intramolecular charge-transfer transition from the donor amino IN atom to the acceptor dinitrobenzene. However, in the presence of coordinating ions such as Cl-, N-3(-), and SCN-, the metal ion comes out of the cavity and binds the cryptand outside the cavity at a site away from the dinitrobenzene moiety. Four such complexes are characterized by X-ray crystallography. Thus, a metal ion can translocate between inside and outside of the cryptand cavity depending upon the nature of the counter anion.