title: Solution and solid state studies on the binding of isomeric carboranes C2B10H12 by p-Bu(t)-calix[5]arene.
abstract: p-Bu(t)-calix[5]arene forms crystalline inclusion complexes with o- and m-carboranes in toluene or dichloromethane-hexane, but not with the p-isomer, the extended structures being based on 1 : 1 host-guest supermolecules, with the p-Bu(t)-substituents creating a snug fit for o- and m-carborane; p-carborane forms a highly hexane soluble complex, induced by grinding, which crystallizes as fibres. Solution phase studies showed the presence of a 1 : 1 host-guest stoichiometry with all three isomeric carboranes as determined from Job plots. The association constants for the o- and m-carborane complexes are 6.4 +/- 0.3 M(-1) and 3.8 +/- 0.1 M(-1) respectively, whereas the p-isomer is only weakly associated. Competition experiments involving all three isomers show rapid exchange on the NMR time scale, and no selectivity in solution is evident. Selective association involving the o- and m-isomers in the solid state is therefore remarkable, and it is a manifestation of crystal packing forces which embodies the differences in dipole moments of the carboranes.
authors.affiliation: School of Biomedical, Biomolecular and Chemical Sciences, University of Western Australia, Crawley, W.A. 6009, Australia.
authors.forename: Thomas E
authors.initials: TE
authors.lastname: Clark
authors.forename: Mohamed
authors.initials: M
authors.lastname: Makha
authors.forename: Colin L
authors.initials: CL
authors.lastname: Raston
authors.forename: Alexandre N
authors.initials: AN
authors.lastname: Sobolev