A series of 12-phenyl-closo-thiaboranes (12-(4-X-C6H4)-closo-1-SB11H10, where X = OMe (2), X = SMe (3), X = Ph (4), and X = NMe2 (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 CO2 to the material crystallized from n-hexane was explained on the basis of cooperative and consecutive machine-like molecular interactions of quadrupolar CO2 molecule with B-H and amino groups inside rectangular cavities.

• Publikační typ
• časopisecké články MeSH

Although 1-Ph-2-X-closo-1,2-C2B10H10 (X = F, Cl, Br, I) derivatives had been computed to have positive values of the heat of formation, it was possible to prepare them. The corresponding solid-state structures were computationally analyzed. Electrostatic potential computations indicated the presence of highly positive σ-holes in the case of heavy halogens. Surprisingly, the halogen•••π interaction formed by the Br atom was found to be more favorable than that of I.

• Klíčová slova
• halogen bond, icosahedral boron cluster, sigma hole,
• MeSH
• halogenace MeSH
• halogeny chemie   MeSH
• molekulární konformace MeSH
• molekulární modely MeSH
• sloučeniny boru chemická syntéza   chemie   MeSH
• techniky syntetické chemie MeSH
• uhlík chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• halogeny MeSH
• sloučeniny boru MeSH
• uhlík MeSH

Chalcogen atoms are a class of substituents capable of generating inner and outer derivatives of boron clusters. It is well known that chalcogenated boron clusters can form strong σ-hole interactions when a chalcogen atom is a part of an icosahedron. This paper studies σ-hole interactions of dicarbaboranes with two exopolyhedral chalcogen atoms bonded to carbon vertices. Specifically, a computational investigation has been carried out on the co-crystal of (1,2-C2B10H10)2Se4•toluene and a single crystal of (1,2-C2B10H10)2Te4.

• Klíčová slova
• co-crystal, heteroborane, sigma hole,
• MeSH
• borany chemie   MeSH
• chalkogeny chemie   MeSH
• krystalizace MeSH
• molekulární modely MeSH
• statická elektřina MeSH
• termodynamika MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• borany MeSH
• chalkogeny MeSH