Pure and Applied Chemistry

Abstract: The study of compounds containing boron continues to have an important impact on virtually every area of chemistry. One of the few areas in which compounds of boron have been neglected is crystal engineering, which seeks to develop and exploit an understanding of how the structure and properties of crystals are related to the individual atomic or molecular components. Although detailed predictions of crystal structures are not yet reliable, crystal engineers have developed a sound qualitative strategy for anticipating and controlling structural preferences. This strategy is based on the design of special molecules, called tectons, which feature carefully selected cores and multiple peripheral functional groups that can direct association and thereby place neighboring molecules in predetermined positions. Recent work has demonstrated that molecular crystals with unique properties can be constructed logically from tectons with boron in their cores or sticky sites of association. In particular, the -B(OH)₂ group of boronic acids engages in reliable patterns of hydrogen bonding, and its use as a sticky site in tectons has emerged as an effective tool for controlling association predictably. In addition, replacement of tetraphenylsilyl or tetraphenylmethyl cores in tectons by tetraphenylborate leaves the overall molecular geometry little changed, but it has the profound effect of introducing charge. Tectons derived from tetraphenylborate can be used rationally to construct porous charged molecular networks that resemble zeolites and undergo selective ion exchange. In such ways, boron offers chemists exciting new ways to engineer molecular crystals with predetermined structures and properties.