ConspectusIn this Account, we discuss our group's research over the past decade on a class of functionalized boron clusters with tunable chemical and physical properties, with an emphasis on accessing and controlling their redox behavior. These clusters can be thought of as three-dimensional aromatic systems that have distinct redox behavior and photophysical properties compared to their two-dimensional organic counterparts. Specifically, our lab has studied the highly tunable, multielectron redox behavior of B₁₂(OR)₁₂ clusters and applied these molecules in various settings. We first discuss the spectroscopic and electrochemical characterization of B₁₂(OR)₁₂ clusters in various oxidation states, followed by their use as catholytes and/or anolytes in redox flow batteries and chemical dopants in conjugated polymers. Additionally, the high oxidizing potential and visible light-absorbing nature of fluoroaryl-functionalized B₁₂(OR)₁₂ clusters have been leveraged by our group to generate weakly coordinating, photoexcitable species that can promote photooxidation chemistry.We have further translated these solution-phase studies of B₁₂(OR)₁₂ clusters to the solid state by using the precursor [B₁₂(OH)₁₂]^2- cluster as a robust building block for hybrid metal oxide materials. Specifically, we have shown that the boron cluster can act as a thermally stable cross-linking material, which enhances electron transport between metal oxide nanoparticles. We applied this structural motif to create TiO₂- and WO₃-containing materials that showed promising properties as photocatalysts and electroactive materials for supercapacitors. Building on this concept, we later discovered that B₁₂(OCH₃)₁₂, the smallest of the B₁₂(OR)₁₂ family, could retain its redox behavior in the solid state, a previously unseen phenomenon. We successfully harnessed this unique behavior for solid-state energy storage by implementing this boron cluster as a cathode-active material in a Li-ion prototype cell device. Recently, our group has also explored how to tune the redox properties of clusters other than B₁₂(OR)₁₂ species by synthesizing a library of vertex-differentiated clusters containing both B-OR and B-halogen groups. Due to the additive qualities of different functional groups on the cluster, these species allow access to a region of electrochemical potentials previously inaccessible by fully substituted closo-dodecaborate alkoxy-based derivatives.Lastly, we discuss our research into smaller-sized redox-active polyhedral boranes (B₆- and B₁₀-based cluster cores). Interestingly, these clusters show significantly less redox stability and reversibility than their dodecaborate-based counterparts. While exploring the functionalization of closo-hexaborate to create fully substituted derivates (i.e., [B₆R₆H^fac]^-), we observed unique oxidative decomposition pathways for this cluster system. Consequently, we leveraged this oxidative instability to generate useful alkyl boronate esters via selective chemical oxidation. We further explored a closo-decaborate cluster as a platform to access electrophilic [B₁₀H₁₃]⁺ species capable of directly borylating arene compounds with unique regioselectivity. Upon chemical oxidation of the arylated decaborate clusters, we successfully synthesized various aryl boronate esters, establishing the generality of the oxidative cluster deconstruction concept.Overall, our work shows that boron clusters are an appealing class of redox-active molecules, and this fundamental and understudied property can be leveraged for constructing novel materials with tunable physical and electrochemical properties, as well as producing unique chemical reagents for small molecule synthesis.

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