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Article Abstract
We report the first paramagnetic boron tetraradical, comprising four boraphenanthrene-type units with boryl radical centers bridged by a central tetraphenylethene (TPE) linker. With strongly π-accepting and sterically demanding cyclic(alkyl)(amino) carbene ligands (), spin densities localize on the boron-carbene fragments (92%), consistent with a true boron-centered tetraradical. Magnetic measurements of reveal minimal spin-spin coupling, consistent with four noninteracting = 1/2 centers. In contrast, weaker π-accepting diamino N-heterocyclic carbene ligands delocalize spin density over the TPE core (88%), yielding a boron-containing hydrocarbon biradical (). Compound exhibits antiferromagnetic interactions (2 = -118 J·mol), supporting an open-shell singlet ground state with a thermally accessible triplet excited state.
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| http://dx.doi.org/10.1021/jacs.5c11428 | DOI Listing |
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