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Abstract
Herein we describe the first main-chain organometallic polymer in which the directionality is not dictated by the poly-N-heterocyclic carbene, but rather that of the precise coordination geometry of metal-sulfide cubane clusters, including a synthetic analogue of biologically ubiquitous, fully ferrous Fe4S4 cubane cluster. These charge-delocalized metal-sulfide cubane clusters are crucial to metalloenzymes yet largely unexplored within the realm of reticular chemistry. Such clusters can also be extracted from the polymers pos-synthetically with excess of the original stabilizing N-heterocyclic carbene (NHC) ligands. The surprising reversibility of these organometallic bonds provides strong evidence for possible modulation synthetic approaches. The discrete cubanes are also shown to form, surprisingly, solution processible superatomic ion pairs with fullerene. Main-chain organometallic polymers (MCOPs) formed from these superatomic ion pairs have electrical conductivities far exceeding that of their constituents or MCOPs formed from other cluster-ion pairs.Lastly, a computational investigation of hexa-substituted [3]radialenes as redox flow battery materials (RFBs) is described. Computational methods were used to better understand the dimerization of a series of cyanoester substituted [3]radialene derivatives. Additionally, preliminary density functional theory (DFT) methods for identifying suitable derivatives for synthesis were investigated. Specific emphasis is placed on readily calculated properties including Mulliken spin density and buried volume. The unifying theme of our research has been tunability. From the superatomic building blocks, N-heterocyclic carbene linkers, to hexa-substituted [3]radialenes our lab has explored constituents with extraordinary degrees of synthetic flexibility. Thus, the broader impacts of this research are not restrained to the specific molecules described within.