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 dimers 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 × 5.9 Å2 and
5.2 × 8.6 Å2 in cross section at the narrowest points, whereas those in crystals of tetraphenylsilane 2 are
approximately 6.4 × 6.4 Å2 and 6.4 × 9.0 Å2. 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) Å) than the C−C bonds at the core of tetraboronic acid 1 (1.519(6)
Å), 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.