화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.125, No.4, 1002-1006, 2003
Molecular tectonics. Use of the hydrogen bonding of boronic acids to direct supramolecular construction
Tetraboronic acids 1 and 2 have four -B(OH)(2) groups oriented tetrahedrally by cores derived from tetraphenylmethane and tetraphenylsilane. Crystallization produces isostructural diamondoid networks held together by hydrogen bonding of the -B(OH)(2) groups, in accord with the tendency of simple arylboronic acids to form cyclic hydrogen-bonded dinners in the solid state. Five-fold interpenetration of the networks is observed, but 60% and 64% of the volumes of crystals of tetraboronic acids 1 and 2, respectively, remain available for the inclusion of disordered guests. Guests occupy two types of interconnected channels aligned with the a and b axes; those in crystals of tetraphenylmethane 1 measure approximately 5.9 x 5.9 Angstrom(2) and 5.2 x 8.6 Angstrom(2) in cross section at the narrowest points, whereas those in Crystals of tetraphenylsilane 2 are approximately 6.4 x 6.4 Angstrom(2) and 6.4 x 9.0 Angstrom(2). These channels provide access to the interior and permit guests to be exchanged quantitatively without loss of crystallinity. Because the Si-C bonds at the core of tetraboronic acid 2 are longer (1.889(3) Angstrom) than the C-C bonds at the core of tetraboronic acid 1 (1.519(6) Angstrom), the resulting network is expanded rationally. By associating to form robust isostructural networks with predictable architectures and properties of porosity, compounds 1 and 2 underscore the usefulness of molecular tectonics as a strategy for making ordered materials.