Conformational Control of benzyl-o-carboranylbenzene derivatives and molecular encapsulation of acetone in the dynamically formed space of 1,3,5-Tris(2-benzyl-o-carboran-1-yl)benzene

Chalermkiat Songkram, Kiminori Ohta, Kentaro Yamaguchi, Fabio Pichierri, Yasuyuki Endo

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)

Abstract

A 1,3,5-substituted benzene platform has been widely used in the fields of supramolecular chemistry and molecular recognition. Here, we show that 1,3,5-tris(2-benzyl-o-carboran-1-yl)benzene 6 exhibits solvent-dependent conformation in the crystalline state. Recrystallization from dichloromethane-n-pentane gave the anti conformation 6-anti, while recrystallization from methanol-acetone gave the syn conformation 6-syn, in which the three benzyl-o-carboranyl moieties are located to one side of the central benzene ring. Interestingly, one acetone molecule is captured in the π-rich space of 6-syn and two complexes facing each other encapsulate two acetone molecules in a π-rich container formed by the eight benzene rings. The inclusion involves several weak interactions, that is, T-shaped C-H⋯π interactions, and C-H⋯O and C-H⋯π interactions. Two C-H⋯O interactions involving benzylic C-H hydrogens activated by the electron-withdrawing character of the o-carborane cage and the oxygen atom of the acetone seem to be the most important. DFT calculations indicate that the binding energy for entrapment of acetone is 6.6 kcal/mol. Inclusion of acetone is achieved through not only multiple C-H⋯O interactions but also a number of C-H⋯π interactions. The third benzyl-o-carborane moiety is fixed in the syn conformation by intramolecular and intermolecular C-H⋯π interactions.

Original languageEnglish
Pages (from-to)11174-11183
Number of pages10
JournalInorganic chemistry
Volume49
Issue number23
DOIs
Publication statusPublished - 2010 Dec 6

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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