Molecular and Electronic Structure, and Hydrolytic Reactivity of a Samarium(II) Crown Ether Complex

Frankie D. White, Cristian Celis-Barros, Jillian Rankin, Eduardo Solís-Céspedes, David Dan, Alyssa N. Gaiser, Yan Zhou, Jasmine Colangelo, Dayán Páez-Hernández, Ramiro Arratia-Pérez, Thomas E. Albrecht-Schmitt

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Resumen

The reaction of SmI 2 with dibenzo-30-crown-10 (DB30C10), followed by metathesis with [Bu 4 N][BPh 4 ], allows for the isolation of [Sm II (DB30C10)][BPh 4 ] 2 as bright-red crystals in good yield. Exposure of [Sm(DB30C10)] 2+ to solvents containing trace water results in the conversion to the dinuclear Sm III complex, Sm 2 (DB30C10)(OH) 2 I 4 . Structural analysis of both complexes shows substantial rearrangement of the crown ether from a folded, Pac-Man form with Sm II to a twisted conformation with Sm III . The optical properties of [Sm II (DB30C10)][BPh 4 ] 2 exhibit a strong temperature dependence and change from broad-band absorption features indicative of domination by 5d states to fine features characteristic of 4f 4f transitions at low temperatures. Examination of the electronic structure of these complexes via ab initio wave function calculations (SO-CASSCF) shows that the ground state of Sm II in [Sm II (DB30C10)] 2+ is a 4f 6 state with low-lying 4f 5 5d 1 states, where the latter states have been lowered in energy by 12 000 cm -1 with respect to the free ion. The decacoordination of the Sm II cation by the crown ether is responsible for this alteration in the energies of the excited state and demonstrates the ability to tune the electronic structure of Sm II .

Idioma originalInglés
Páginas (desde-hasta)3457-3465
Número de páginas9
PublicaciónInorganic Chemistry
Volumen58
N.º5
DOI
EstadoPublicada - 4 mar 2019

Áreas temáticas de ASJC Scopus

  • Química física y teórica
  • Química inorgánica

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    White, F. D., Celis-Barros, C., Rankin, J., Solís-Céspedes, E., Dan, D., Gaiser, A. N., Zhou, Y., Colangelo, J., Páez-Hernández, D., Arratia-Pérez, R., & Albrecht-Schmitt, T. E. (2019). Molecular and Electronic Structure, and Hydrolytic Reactivity of a Samarium(II) Crown Ether Complex. Inorganic Chemistry, 58(5), 3457-3465. https://doi.org/10.1021/acs.inorgchem.8b03566