Surface-induced spin state locking of the [Fe(H2B(pz)2)2(bipy)] spin crossover complex

J Phys Condens Matter. 2016 May 25;28(20):206002. doi: 10.1088/0953-8984/28/20/206002. Epub 2016 Apr 28.

Abstract

Temperature- and coverage-dependent studies of the Au(1 1 1)-supported spin crossover Fe(II) complex (SCO) of the type [Fe(H2B(pz)2)2(bipy)] with a suite of surface-sensitive spectroscopy and microscopy tools show that the substrate inhibits thermally induced transitions of the molecular spin state, so that both high-spin and low-spin states are preserved far beyond the spin transition temperature of free molecules. Scanning tunneling microscopy confirms that [Fe(H2B(pz)2)2(bipy)] grows as ordered, molecular bilayer islands at sub-monolayer coverage and as disordered film at higher coverage. The temperature dependence of the electronic structure suggest that the SCO films exhibit a mixture of spin states at room temperature, but upon cooling below the spin crossover transition the film spin state is best described as a mix of high-spin and low-spin state molecules of a ratio that is constant. This locking of the spin state is most likely the result of a substrate-induced conformational change of the interfacial molecules, but it is estimated that also the intra-atomic electron-electron Coulomb correlation energy, or Hubbard correlation energy U, could be an additional contributing factor.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.
  • Research Support, Non-U.S. Gov't