Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes

Controlling the properties of heavy element complexes, such as those containing berkelium, is challenging because relativistic effects, spin-orbit and ligand-field splitting, and complex metal-ligand bonding, all dictate the final electronic states of the molecules. While the first two of these are currently beyond experimental control, covalent M‒L interactions could theoretically be boosted through the employment of chelators with large polarizabilities that substantially shift the electron density in the molecules. This theory is tested by ligating BkIII with 4’-(4-nitrophenyl)-2,2’:6’,2”-terpyridine (terpy*), a ligand with a large dipole. The resultant complex, Bk(terpy*)(NO3)3(H2O)·THF, is benchmarked with its closest electro chemical analog, Ce(terpy*)(NO3)3(H2O)·THF. Here, we show that enhanced Bk‒N inter actions with terpy* are observed as predicted. Unexpectedly, induced polarization by terpy* also creates a plane in the molecules wherein the M‒L bonds trans to terpy* are shorter than anticipated. Moreover, these molecules are highly anisotropic and rhombic EPR spectra for the CeIII complex are reported.

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Indexación: Scopus.

Keywords

Berkelium, Computational Chemistry, Nuclear Chemistry, Solid-state Chemistry, Electrochemical Data, Terpyridine, cerium(III), CeIII

Citation

Nature Communications Volume 12, Issue 1December 2021 Article number 7230

DOI

10.1038/s41467-021-27576-y

URI

https://repositorio.unab.cl/xmlui/handle/ria/48749

Collections

FCE - Artículos de Revista

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