Our laboratory has been interested in the synthesis, chemical reactivity, and optical properties of main-group element-centered molecules. Compared to the d-block elements, those of the s- and p-blocks often require specialized ligands and experimental techniques to isolate suitable compounds that undergo redox transformations and/or activate chemical bonds. Indeed, there are inherent differences in the frontier molecular orbitals of main-group and transition metal compounds and many main-group elements exhibit thermodynamically weaker bonding. However, exploiting these unusual bonding situations can lead to new molecules that are important for small molecule activation, catalysis, and the design functional materials. We have isolated a family of stibenium and bismuthenium ions with highly unusual C=Pn+ (Pn = Sb, Bi) multiple bonding. Our goal is to tune the Lewis acidity of heavy pnictogen cations such that they promote electrophilic bond activation. All of these compounds feature relatively earth-abundant and cost-effective elements. In a separate project, we have been exploring the chemistry of borafluorenes, borepins, and related boron-doped polycyclic aromatic hydrocarbons (PAHs) with extended π-systems. We have prepared reduced boron compounds that promote CO2 activation and have realized some of the first examples of borenium ion-based stimuli-responsive materials. Recently, we designed air-stable borafluorenium ions that emit over a wide temperature range, even showing white-light emission and near-room temperature activity. This presentation will highlight our most recent results in these research areas.

Award Address (Harry Gray Award for Creative Work in Inorganic Chemistry by a Young Investigator sponsored by the Gray Award Endowment). Main-group renaissance: From unusual bonding to functional materials

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