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

doi:10.1021/acs.inorgchem.8b03566

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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Abstract

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 .

Original language	English
Pages (from-to)	3457-3465
Number of pages	9
Journal	Inorganic Chemistry
Volume	58
Issue number	5
DOIs	https://doi.org/10.1021/acs.inorgchem.8b03566
State	Published - Mar 4 2019
Externally published	Yes

Funding

This joint work was supported as part of the Center for Actinide Science and Technology (CAST), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award Number DE-SC0016568 and the Heavy Elements Chemistry Program (HEC) under Award Number DE-FG02-13ER16414. CAST provided the computational aspects of the research while (HEC) provided the experimental research. Part of the computational calculations were provided by Fondecyt 1180017 and Fondecyt 1150629 grants.

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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

@article{35c5eb7eb48745729627d2bd3ff3d491,

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

abstract = " 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 .",

author = "White, {Frankie D.} and Cristian Celis-Barros and Jillian Rankin and Eduardo Sol{\'i}s-C{\'e}spedes and David Dan and Gaiser, {Alyssa N.} and Yan Zhou and Jasmine Colangelo and Day{\'a}n P{\'a}ez-Hern{\'a}ndez and Ramiro Arratia-P{\'e}rez and Albrecht-Schmitt, {Thomas E.}",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

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doi = "10.1021/acs.inorgchem.8b03566",

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White, FD , Celis-Barros, C, Rankin, J, Solís-Céspedes, E, Dan, D, Gaiser, AN, Zhou, Y, Colangelo, J, Páez-Hernández, D, Arratia-Pérez, R & Albrecht-Schmitt, TE 2019, 'Molecular and Electronic Structure, and Hydrolytic Reactivity of a Samarium(II) Crown Ether Complex', Inorganic Chemistry, vol. 58, no. 5, pp. 3457-3465. https://doi.org/10.1021/acs.inorgchem.8b03566

TY - JOUR

T1 - Molecular and Electronic Structure, and Hydrolytic Reactivity of a Samarium(II) Crown Ether Complex

AU - White, Frankie D.

AU - Celis-Barros, Cristian

AU - Rankin, Jillian

AU - Solís-Céspedes, Eduardo

AU - Dan, David

AU - Gaiser, Alyssa N.

AU - Zhou, Yan

AU - Colangelo, Jasmine

AU - Páez-Hernández, Dayán

AU - Arratia-Pérez, Ramiro

AU - Albrecht-Schmitt, Thomas E.

PY - 2019/3/4

Y1 - 2019/3/4

N2 - 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 .

AB - 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 .

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U2 - 10.1021/acs.inorgchem.8b03566

DO - 10.1021/acs.inorgchem.8b03566

M3 - Article

C2 - 30788962

AN - SCOPUS:85062430138

SN - 0020-1669

VL - 58

SP - 3457

EP - 3465

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 5

ER -

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

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