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

Journal Article · · Inorganic Chemistry
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)
+ Show Author Affiliations

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.

Research Organization:
Florida State Univ., Tallahassee, FL (United States); Univ. of Texas, Austin, TX (United States). Energy Frontier Research Center (EFRC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0010677; SC0016568
OSTI ID:
1566507
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 5 Vol. 58; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (36)

Relativistic regular two-component Hamiltonians journal February 1996
Oxidatively Stable, Aqueous Europium(II) Complexes through Steric and Electronic Manipulation of Cryptand Coordination Chemistry journal October 2010
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
Lanthanide(II) Complexes Supported by N,O-Donor Tripodal Ligands: Synthesis, Structure, and Ligand-Dependent Redox Behavior journal August 2015
Relativistic Hamiltonians for Chemistry: A Primer journal November 2011
The ORCA program system: The ORCA program system journal June 2011
Ligand spin polarization and antiferromagnetic coupling in transition metal dimers journal November 1986
DFT calculations of molecular magnetic properties of coordination compounds journal March 2003
Coordination chemistry and structure characterization of C18H36O6N2Eu2(NO3)6·H2O journal July 1987
Synthesis and structure characterization of lanthanum [2,2,2]cryptates, [LaCl[2,2,2](H2O)] Cl2 · H2O and [La(CF3SO3)[2,2,2](DMF)](CF3SO3)2 journal January 1994
Studies on crown ether complexes—XXX. Synthesis, properties and structure of the 3:2 complexes of heavier lanthanide nitrates (Sm-Lu) with dibenzo-30-crown-10 journal September 1993
MOLCAS: a program package for computational chemistry journal October 2003
Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States journal September 2016
From a Piano Stool to a Sandwich: A Stepwise Route for Improving the Slow Magnetic Relaxation Properties of Thulium journal August 2017
Structural investigation into the steric control of polyether complexation in the lanthanide series: macrocyclic 18-crown-6 versus acyclic pentaethylene glycol journal August 1993
Spin Densities and Spin Coupling in Iron-Sulfur Clusters: A New Analysis of Hyperfine Coupling Constants journal August 1995
Supramolecular Chemistry of p-Sulfonatocalix[5]arene: A Water-Soluble, Bowl-Shaped Host with a Large Molecular Cavity journal November 1995
Electronic structure of 2-Fe ferredoxin models by X.alpha. valence bond theory journal June 1980
Concentration-Independent pH Detection with a Luminescent Dimetallic Eu(III)-Based Probe journal October 2012
Aqueous Eu II -Containing Complex with Bright Yellow Luminescence journal April 2015
Tunable Luminescent Lanthanide Supramolecular Assembly Based on Photoreaction of Anthracene journal May 2017
Controlled Photophysical Behaviors between Dibenzo-24-crown-8 Bearing Terpyridine Moiety and Fullerene-Containing Ammonium Salt journal March 2011
A Reversible Luminescent Lanthanide Switch Based on a Dibenzo[24]-Crown-8−Dipicolinic Acid Conjugate journal November 2008
Two complexes of Sm( ii ) with crown ethers—electrochemical synthesis, structure and spectroscopy journal January 2004
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
Displacement of a cyclopentadienyl ligand by a crown ether from a lanthanocene(ii) [LnCp′′2]; crystal structures of the first cationic lanthanoid(ii) complexes, [SmCp′′([18]-crown-6)][SmCp′′3]·0.5C6H6 and [YbCp′′([18]-crown-6)][Cp′′]·3C6H6 [Cp′′ = η5-C5H3(SiMe3)2-1,3] journal January 1998
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
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
Valence bond description of antiferromagnetic coupling in transition metal dimers journal May 1981
f   d transition energies of divalent lanthanides in inorganic compounds journal January 2003
Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation journal June 1986
Generalized Gradient Approximation Made Simple journal October 1996
OLEX2 : a complete structure solution, refinement and analysis program journal January 2009
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
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
SHELXT – Integrated space-group and crystal-structure determination journal January 2015

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