Electronic structure modulation in an exceptionally stable non-heme nitrosyl iron(II) spin-crossover complex

L. Pineiro-Lopez (1) , Norma Ortega-Villar (2) , M. Carmen Munoz (3) , Gábor Molnár (4) , Jordi Cirera (5) , Rafael Moreno-Esparza (2) , Victor M. Ugalde-Saldivar (2) , Azzedine Bousseksou (4) , E. Ruiz (6) , J. A. Real (1)

1 ICMol - Instituto de Ciencia Molecular
2 Facultad de Quimica, Universidad Nacional Autonoma de Mexico
3 UPV - Universitat Politècnica de València = Universitad Politecnica de Valencia = Polytechnic University of Valencia
4 LCC - Laboratoire de chimie de coordination
5 Institut de Recerca de Química Teorica i Computacional
6 UAB - Universitat Autònoma de Barcelona = Autonomous University of Barcelona = Universidad Autónoma de Barcelona

The highly stable nitrosyl iron(II) mononuclear complex [Fe(bztpen)(NO)](PF6)(2) (bztpen=N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethylenediamine) displays an S=1/2 <-> S=3/2 spin crossover (SCO) behavior (T-1/2=370 K, Delta H= 12.48 kJmol(-1), Delta S=33 JK(-1) mol(-1)) stemming from strong magnetic coupling between the NO radical (S=1/2) and thermally interconverted (S=0 <-> S=2) ferrous spin states. The crystal structure of this robust complex has been investigated in the temperature range 120-420 K affording a detailed picture of how the electronic distribution of the t(2g)-e(g) orbitals modulates the structure of the FeNO(7) bond, providing valuable magneto-structural and spectroscopic correlations and DFT analysis.

Domaines: Chimie de coordination

L. Pineiro-Lopez, Norma Ortega-Villar, M. Carmen Munoz, Gábor Molnár, Jordi Cirera, et al.. Electronic structure modulation in an exceptionally stable non-heme nitrosyl iron(II) spin-crossover complex. Chemistry - A European Journal, 2016, 22 (36), pp.12741-12751. ⟨10.1002/chem.201601172⟩. ⟨hal-01934973⟩