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

Abstract

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.

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)
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. 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, and Albrecht-Schmitt, Thomas E. Thu . "Molecular and Electronic Structure, and Hydrolytic Reactivity of a Samarium(II) Crown Ether Complex". United States. https://doi.org/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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Works referenced in this record:

Synthesis of rare-earth-metal-in-cryptand dications, [Ln(2.2.2-cryptand)] 2+ , from Sm 2+ , Eu 2+ , and Yb 2+ silyl metallocenes (C 5 H 4 SiMe 3 ) 2 Ln(THF) 2
journal, January 2017

  • Huh, Daniel N.; Kotyk, Christopher M.; Gembicky, Milan
  • Chemical Communications, Vol. 53, Issue 62
  • DOI: 10.1039/C7CC04396A

Oxidatively Stable, Aqueous Europium(II) Complexes through Steric and Electronic Manipulation of Cryptand Coordination Chemistry
journal, October 2010

  • Gamage, Nipuni-Dhanesha H.; Mei, Yujiang; Garcia, Joel
  • Angewandte Chemie International Edition, Vol. 49, Issue 47
  • DOI: 10.1002/anie.201002789

Lanthanide(II) Complexes Supported by N,O-Donor Tripodal Ligands: Synthesis, Structure, and Ligand-Dependent Redox Behavior
journal, August 2015

  • Andrez, Julie; Bozoklu, Gülay; Nocton, Grégory
  • Chemistry - A European Journal, Vol. 21, Issue 43
  • DOI: 10.1002/chem.201502204

A Reversible Luminescent Lanthanide Switch Based on a Dibenzo[24]-Crown-8−Dipicolinic Acid Conjugate
journal, November 2008

  • Han, Min; Zhang, Heng-Yi; Yang, Li-Xu
  • Organic Letters, Vol. 10, Issue 24
  • DOI: 10.1021/ol802376k

Controlled Photophysical Behaviors between Dibenzo-24-crown-8 Bearing Terpyridine Moiety and Fullerene-Containing Ammonium Salt
journal, March 2011

  • Ding, Zhi-Jun; Zhang, Ying-Ming; Teng, Xue
  • The Journal of Organic Chemistry, Vol. 76, Issue 6
  • DOI: 10.1021/jo102311m

Tunable Luminescent Lanthanide Supramolecular Assembly Based on Photoreaction of Anthracene
journal, May 2017

  • Zhou, Yan; Zhang, Heng-Yi; Zhang, Zhi-Yuan
  • Journal of the American Chemical Society, Vol. 139, Issue 21
  • DOI: 10.1021/jacs.7b03153

Aqueous Eu II -Containing Complex with Bright Yellow Luminescence
journal, April 2015

  • Kuda-Wedagedara, Akhila N. W.; Wang, Chengcheng; Martin, Philip D.
  • Journal of the American Chemical Society, Vol. 137, Issue 15
  • DOI: 10.1021/jacs.5b02506

Concentration-Independent pH Detection with a Luminescent Dimetallic Eu(III)-Based Probe
journal, October 2012

  • Moore, Jeremiah D.; Lord, Richard L.; Cisneros, G. Andrés
  • Journal of the American Chemical Society, Vol. 134, Issue 42
  • DOI: 10.1021/ja307098z

Supramolecular Chemistry of p-Sulfonatocalix[5]arene: A Water-Soluble, Bowl-Shaped Host with a Large Molecular Cavity
journal, November 1995

  • Steed, Jonathan W.; Johnson, Carl P.; Barnes, Charles L.
  • Journal of the American Chemical Society, Vol. 117, Issue 46
  • DOI: 10.1021/ja00151a006

Structural investigation into the steric control of polyether complexation in the lanthanide series: macrocyclic 18-crown-6 versus acyclic pentaethylene glycol
journal, August 1993

  • Rogers, Robin D.; Rollins, Andrew N.; Etzenhouser, Russell D.
  • Inorganic Chemistry, Vol. 32, Issue 16
  • DOI: 10.1021/ic00068a013

Two complexes of Sm( ii ) with crown ethers—electrochemical synthesis, structure and spectroscopy
journal, January 2004


OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009

  • Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
  • Journal of Applied Crystallography, Vol. 42, Issue 2
  • DOI: 10.1107/S0021889808042726

SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053273314026370

Relativistic Hamiltonians for Chemistry: A Primer
journal, November 2011


Relativistic regular two-component Hamiltonians
journal, February 1996


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation
journal, June 1986


The X α valence bond theory of weak electronic coupling. Application to the low‐lying states of Mo 2 Cl 8 4−
journal, June 1979

  • Noodleman, Louis; Norman, Joe G.
  • The Journal of Chemical Physics, Vol. 70, Issue 11
  • DOI: 10.1063/1.437369

Valence bond description of antiferromagnetic coupling in transition metal dimers
journal, May 1981

  • Noodleman, Louis
  • The Journal of Chemical Physics, Vol. 74, Issue 10
  • DOI: 10.1063/1.440939

Electronic structure of 2-Fe ferredoxin models by X.alpha. valence bond theory
journal, June 1980

  • Norman, Joe G.; Ryan, P. Barry; Noodleman, Louis
  • Journal of the American Chemical Society, Vol. 102, Issue 12
  • DOI: 10.1021/ja00532a060

Ligand spin polarization and antiferromagnetic coupling in transition metal dimers
journal, November 1986


Spin Densities and Spin Coupling in Iron-Sulfur Clusters: A New Analysis of Hyperfine Coupling Constants
journal, August 1995

  • Mouesca, J. -M.; Noodleman, L.; Case, D. A.
  • Inorganic Chemistry, Vol. 34, Issue 17
  • DOI: 10.1021/ic00121a013

MOLCAS: a program package for computational chemistry
journal, October 2003


The ORCA program system: The ORCA program system
journal, June 2011

  • Neese, Frank
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1
  • DOI: 10.1002/wcms.81

Structure and properties of some lanthanoid(III) perchlorates with the cryptand 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane
journal, January 1979

  • Ciampolini, Mario; Dapporto, Paolo; Nardi, Nicoletta
  • Journal of the Chemical Society, Dalton Transactions, Issue 6
  • DOI: 10.1039/dt9790000974

Coordination chemistry and structure characterization of C18H36O6N2Eu2(NO3)6·H2O
journal, July 1987


Reaction between dibenzo-30-crown-10 and potassium thiocyanate; structures of the 1:1 complexes, anhydrous and monohydrated, [K(C28H40O10)]+.SCN− and [K(C28H40O10)]+.SCN−.H2O
journal, September 1984

  • Owen, J. D.; Truter, M. R.; Wingfield, J. N.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 40, Issue 9
  • DOI: 10.1107/S0108270184008568

The structure of a complex between rubidium thiocyanate, water and dibenzo[b,q][1,4,7,10,13,16,19,22,25,28]decaoxacyclotriacontane (dibenzo-30-crown-10)
journal, February 1979

  • Hašek, J.; Huml, K.; Hlavatá, D.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 35, Issue 2
  • DOI: 10.1107/S0567740879003472

Axially Symmetric U−O−Ln- and U−O−U-Containing Molecules from the Control of Uranyl Reduction with Simple f-Block Halides
journal, August 2017

  • Arnold, Polly L.; Cowie, Bradley E.; Suvova, Markéta
  • Angewandte Chemie International Edition, Vol. 56, Issue 36
  • DOI: 10.1002/anie.201705197

From a Piano Stool to a Sandwich: A Stepwise Route for Improving the Slow Magnetic Relaxation Properties of Thulium
journal, August 2017


DFT calculations of molecular magnetic properties of coordination compounds
journal, March 2003


f   d transition energies of divalent lanthanides in inorganic compounds
journal, January 2003