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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 4N][BPh 4], allows for the isolation of [Sm II(DB30C10)][BPh 4] 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, Sm 2(DB30C10)(OH) 2I 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. 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 4f 6 state with low-lying 4f 55d 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 statemore » and demonstrates the ability to tune the electronic structure of Sm II.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [2];  [1];  [1]; ORCiD logo [1];  [1];  [2];  [2]; ORCiD logo [1]
  1. Florida State Univ., Tallahassee, FL (United States)
  2. Andrés Bello National Univ., Santiago (Chile)
Publication Date:
Research Org.:
Univ. of Texas, Austin, TX (United States). Energy Frontier Research Center (EFRC); Florida State Univ., Tallahassee, FL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1566507
Grant/Contract Number:  
SC0010677; SC0016568; FG02-13ER16414
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 58; Journal Issue: 5; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

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, and Albrecht-Schmitt, Thomas E. Molecular and Electronic Structure, and Hydrolytic Reactivity of a Samarium(II) Crown Ether Complex. United States: N. p., 2019. Web. doi: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. United States. doi: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, and Albrecht-Schmitt, Thomas E. Thu . "Molecular and Electronic Structure, and Hydrolytic Reactivity of a Samarium(II) Crown Ether Complex". United States. doi:10.1021/acs.inorgchem.8b03566. https://www.osti.gov/servlets/purl/1566507.
@article{osti_1566507,
title = {Molecular and Electronic Structure, and Hydrolytic Reactivity of a Samarium(II) Crown Ether Complex},
author = {White, Frankie D. and Celis-Barros, Cristian and Rankin, Jillian and Solís-Céspedes, Eduardo and Dan, David and Gaiser, Alyssa N. and Zhou, Yan and Colangelo, Jasmine and Páez-Hernández, Dayán and Arratia-Pérez, Ramiro and Albrecht-Schmitt, Thomas E.},
abstractNote = {The reaction of SmI2 with dibenzo-30-crown-10 (DB30C10), followed by metathesis with [Bu4N][BPh4], allows for the isolation of [SmII(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 SmIII complex, Sm2(DB30C10)(OH)2I4. Structural analysis of both complexes shows substantial rearrangement of the crown ether from a folded, Pac-Man form with SmII to a twisted conformation with SmIII. The optical properties of [SmII(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 SmII in [SmII(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 SmII 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 SmII.},
doi = {10.1021/acs.inorgchem.8b03566},
journal = {Inorganic Chemistry},
number = 5,
volume = 58,
place = {United States},
year = {2019},
month = {2}
}

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