Abstract
A series of 12-phenyl-closo-thiaboranes (12-(4-X-C(6)H(4))-closo-1-SB(11)H(10), where X = OMe (2), X = SMe (3), X = Ph (4), and X = NMe(2) (5)) has been prepared. Except for 2, all compounds exhibit a chalcogen bond of thiaborane to the phenyl ring or the neighboring molecule as major supramolecular structural motif. 5, having the strongest (-12.47 kcal/mol) structure-making intermolecular interaction via noncovalent S···π(phenyl) chalcogen bond, was crystallized from different solvents in the form of various solvatopolymorphs. n-Hexane and diethyl ether can be removed from 5 easily upon the formation of a porous material with large cavities (up to 20.5% of the unit cell). This first stable and useful noncovalently bound organic framework material with an ultramicroporous structure exhibits a molecular sieve effect. The selective and repeatable adsorption of CO(2) to the material crystallized from n-hexane was explained on the basis of cooperative and consecutive machine-like molecular interactions of quadrupolar CO(2) molecule with B-H and amino groups inside rectangular cavities.