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

Inorganic Chemistry
Frankie D WhiteThomas E Albrecht-Schmitt

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. 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. Examination of the electronic structure of these complexes via ab initio wave function calculations (SO-CASSCF) shows 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 structu...Continue Reading

References

Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Jul 15, 2004·Dalton Transactions : an International Journal of Inorganic Chemistry·Przemysław Starynowicz
Nov 15, 2011·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Trond Saue
Oct 17, 2012·Journal of the American Chemical Society·Jeremiah D MooreMatthew J Allen
Dec 30, 2014·Acta Crystallographica. Section A, Foundations and Advances·George M Sheldrick
Apr 9, 2015·Journal of the American Chemical Society·Akhila N W Kuda-WedagedaraMatthew J Allen
May 17, 2017·Journal of the American Chemical Society·Yan ZhouYu Liu

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Citations

May 21, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·María Joaquina Beltrán-LeivaDayán Páez-Hernández

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