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

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

doi:10.1021/acs.inorgchem.8b03566

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

Journal Article · Thu Feb 21 00:00:00 EST 2019 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.8b03566· OSTI ID:1566507

^[1];

^[1]; Rankin, Jillian ^[1];

^[2]; Dan, David ^[1]; Gaiser, Alyssa N. ^[1];

^[1]; Colangelo, Jasmine ^[1]; Páez-Hernández, Dayán ^[2]; Arratia-Pérez, Ramiro ^[2];

^[1]

Florida State Univ., Tallahassee, FL (United States)
Andrés Bello National Univ., Santiago (Chile)

The reaction of SmI₂ with dibenzo-30-crown-10 (DB30C10), followed by metathesis with [Bu₄N][BPh₄], allows for the isolation of [Sm^II(DB30C10)][BPh₄]₂ as bright-red crystals in good yield. Moreover, exposure of [Sm(DB30C10)]²⁺ to solvents containing trace water results in the conversion to the dinuclear Sm^III complex, Sm₂(DB30C10)(OH)₂I₄. 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)][BPh₄]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. Here, exploration of the electronic structure of these complexes via ab initio wave function calculations (SO-CASSCF) reflects that the ground state of Sm^II in [Sm^II(DB30C10)]²⁺ is a 4f⁶ state with low-lying 4f⁵5d¹ 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.

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Research Organization:: Univ. of Texas, Austin, TX (United States). Energy Frontier Research Center (EFRC); Florida State Univ., Tallahassee, FL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0010677; SC0016568; FG02-13ER16414

OSTI ID:: 1566507

Journal Information:: Inorganic Chemistry, Vol. 58, Issue 5; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 8 works

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

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