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

Research output: Contribution to journalArticle

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 languageEnglish
Pages (from-to)3457-3465
Number of pages9
JournalInorganic Chemistry
Volume58
Issue number5
DOIs
Publication statusPublished - 4 Mar 2019

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Samarium
Crown Ethers
samarium
Molecular structure
Electronic structure
ethers
molecular structure
reactivity
electronic structure
metathesis
structural analysis
isolation
examination
wave functions
broadband
optical properties
cations
temperature dependence
ground state
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

White, F. D., Celis-Barros, C., Rankin, J., Solís-Céspedes, E., Dan, D., Gaiser, A. N., ... 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
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. / Molecular and Electronic Structure, and Hydrolytic Reactivity of a Samarium(II) Crown Ether Complex. In: Inorganic Chemistry. 2019 ; Vol. 58, No. 5. pp. 3457-3465.
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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 .",
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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

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.

In: Inorganic Chemistry, Vol. 58, No. 5, 04.03.2019, p. 3457-3465.

Research output: Contribution to journalArticle

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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.

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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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White FD, Celis-Barros C, Rankin J, Solís-Céspedes E, Dan D, Gaiser AN et al. Molecular and Electronic Structure, and Hydrolytic Reactivity of a Samarium(II) Crown Ether Complex. Inorganic Chemistry. 2019 Mar 4;58(5):3457-3465. https://doi.org/10.1021/acs.inorgchem.8b03566