Analysis of Lanthanide-Radical Magnetic Interactions in Ce(III) 2,2′-Bipyridyl Complexes

Fabrizio Ortu, Jingjing Liu, Matthew Burton, Jonathan M. Fowler, Alasdair Formanuik, Marie-Emmanuelle Boulon, Nicholas Chilton, David Mills

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    Abstract

    A series of lanthanide complexes bearing organic radical ligands, [Ln(CpR)2(bipy·–)] [Ln = La, CpR = Cptt (1); Ln = Ce, CpR = Cptt (2); Ln = Ce, CpR = Cp″ (3); Ln = Ce, CpR = Cp‴ (4)] [Cptt = {C5H3tBu2-1,3}−; Cp″ = {C5H3(SiMe3)2-1,3}−; Cp‴ = {C5H2(SiMe3)3-1,2,4}−; bipy = 2,2′-bipyridyl], were prepared by reduction of [Ln(CpR)2(μ-I)]2 or [Ce(Cp‴)2(I) (THF)] with KC8 in the presence of bipy (THF = tetrahydrofuran). Complexes 1–4 were thoroughly characterized by structural, spectroscopic, and computational methods, together with magnetism and cyclic voltammetry, to define an unambiguous Ln(III)/bipy·– radical formulation. These complexes can act as selective reducing agents; for example, the reaction of 3 with benzophenone gives [{Ce(Cp”)2(bipy)}2{κ2-O,O′-OPhC(C6H5)CPh2O}] (7), a rare example of a “head-to-tail” coupling product. We estimate the intramolecular exchange coupling for 2–4 using multiconfigurational and spin Hamiltonian methods and find that the commonly used Lines-type isotropic exchange is not appropriate, even for single 4f e–/organic radical pairs.
    Original languageEnglish
    Pages (from-to)2496–2505
    Number of pages10
    JournalInorganic Chemistry
    Volume56
    Issue number5
    Early online date16 Feb 2017
    DOIs
    Publication statusPublished - 6 Mar 2017

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