Self-Assembly of Grid and Helical Hydrogen-Bonded Arrays Incorporating Bowl-Shaped Receptor Sites That Bind Globular Molecules

Abstract

1,2-Dicarbadodecaborane(12) (o-carborane) and bowl-shaped cyclotriveratrylene (CTV) self-assemble through bifurcated C ± H carborane´´´( O) 2 hydrogen bonds into infinite arrays with two-dimensional (2D) hexagonal grid or helical chain topologies. The in-built shape-specific receptor sites bind o-carborane or fullerene C 70 . The structures of two such supramolecular systems in the solid state were established: (ocarborane) 2 (CTV) features hydrogenbonded carborane´´´CTV hexagonal grids as well as CTV´´´carborane host ± guest interactions, while a helical hydrogen-bonded carborane´´´CTV chain is formed in the quaternary system (C 70 )(o-carborane)(CTV)(1,2-dichlorobenzene) in addition to CTV´´´C 70 host ± guest interactions. The bifurcated C ± H carborane´´´( O) 2 hydrogen bonding interaction common to both these structures was studied on the model system (o-carborane)(1,2-dimethoxybenzene) using ab initio calculations and found to be energetically favoured by 5.48 kcal mol À1

Carboranes as guests, counterions and linkers in coordination polymers and networks

“…The transition from simple hostguest assembly with discrete domains [6] to coordination polymer [7] is made by …”

Cavity-Assembled Porous Solids (CAPSs) for Nanospace-Specific Functions

“…For example, CTV molecules form stacked columns, and further packing of these columns results in the formation of a channel structure capable of guest accommodation. 31,32 Moreover, Raston and Hardie have found that CTV can also form network crystal structures mediated by hydrogen bonding with o-carborane 33 or by complexation with alkali cations 34 at their veratrole parts. In the structures of coordination polymers, the cavity of cyclotriveratrylene serves as recognition sites for several spherical anions such as halogenated carbaborane anions 35 is not encapsulated in the cavity of CTV directly but sandwiched by two CTV molecules to form a loose capsule-like structure, and the disordered CH 3 CN molecules are placed in the cavity of CTV.…”

Cyclotriveratrylene Dendrimers with a Fullerene C60 in the Dendritic Branches

“…The cup-shaped cyclotriveratrylene derivatives (CTV) are among the key structures that have been exploited for many years for the design of molecular hosts [1][2][3][4][5][6][7]. They are interesting starting compounds for the construction of new macromolecular architectures such as solid inclusion complexes [8], biosensors, bis-cryptophanes to study the guest…”