(Ethylenediamine)Pt(uracilate)](4), a Metal Analogue of Calix[4]arene. Coordination and Anion Host-Guest Chemistry Related to Its Conformational Dynamics.

Abstract

The open "molecular box" [(en)Pt(UH-N(1),N(3))](4)(NO(3))(4) (with en = 1,2-diaminoethane, UH = uracil monoanion) resembles calix[4]arenes in its structure and solution dynamics. It adopts a 1,3-alternate conformation in the solid-state (1a), but in solution and after deprotonation to [(en)Pt(U-N(1),N(3))](4), a second major species (cone conformer (1b-4H(+))) occurs. 1b-4H(+) acts as an efficient ligand for additional metal ions through the oxo-surface formed by the four O(2) exocyclic atoms of the uracil nucleobases. As shown here, 1b-4H(+) can incorporate a single metal ion only, giving rise to the formation of species of type {[(en)PtU](4)M}(X)(n)() with M = Zn(II) (2a), Be(II) (3) (not isolated in the solid state), and La(III) (4); X = NO(3), SO(4)/2; n = 2, 3. In addition, both the protonated species of the cone conformer (1b, pH 2-4) and compounds 2a (at pH 3-8) and 3 (at pH 3-5) act as hosts for organic anions in water, as deduced from (1)H NMR studies. It is proposed that the cone conformers act as anion hosts due to a combination of positive charge as well as apolarity and size of the cavity. Host-guest complexes of type {[(en)PtU](4)Zn}(X)(NO(3),SO(4)/2) with X = p-toluenesulfonate (2b) and 3-(trismethylsilyl)-1-propanesulfonate (2c) included in the cone cavity have been prepared and association constants have been determined by (1)H NMR spectroscopy. The fact that 4 does not act as a host may be due to a possible tetradentate coordination of La to 1b-4H(+) which may result in a flatter cone cavity than in compounds 2 and 3.