A tetrahedral four-center–one-electron lanthanide–lanthanide bond

Résumé fourni par la source

Direct lanthanide–lanthanide bonding has been so far established only in two- and threecenter systems. Here we report lanthanide complexes containing a tetrahedral Ln4 core featuring a four-center–one-electron (4c–1e) lanthanide–lanthanide bond. In a two-step reductive assembly, six-electron reduction of hexaphenylbenzene (HPB) generates a geometrically reorganized HPB6– framework that provides a multimetal-binding environment for assembly of a core comprising four LnII centers and one additional electron. Structural, spectroscopic, magnetic, and computational analyses show that this electron occupies a diffuse cluster orbital of mixed Ln 6s/6p/5d character and is delocalized over the four central metal centers. These results establish a three-dimensional regime of single-electron Ln–Ln bonding and demonstrate how deeply reduced molecular carbon frameworks can access unconventional f-element electronic structures.

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