Stephen M. Holmes

Reversible Thermally and Photoinduced Electron Transfer in a Cyano‐Bridged {Fe2Co2} Square Complex

Flip to be square: Structural, spectroscopic, magnetic, and photomagnetic studies conclusively demonstrate that a tetranuclear cyanometalate {Fe2Co2} complex undergoes reversible thermally and light-induced changes in optical and magnetic properties. This instability is induced by an intramolecular electron transfer, as oberved in three-dimensional Co/Fe Prussian blue compounds (see picture).

Controlling thermally induced electron transfer in cyano-bridged molecular squares: from solid state to solution.

A new cyano-based {Fe 2 Co 2 } complex has been synthesized, and its optical and magnetic properties described in the frame of an intramolecular electron transfer. Due to methyl functionalization of the ligand, which gives good solubility to this complex, its thermally induced switchable behavior has been transferred to solution and finely tuned over a broad temperature range by adjusting the solvent composition and polarity.

Pyrazolylborates and Their Importance in Tuning Single-Molecule Magnet Properties of {FeIII2NiII} Complexes

A new tricyanoferrate(III) building block and a trinuclear single-molecule magnet derivative are described. The treatment of a 2:1 ratio of [NEt(4)][(Tp*(Bn))Fe(III)(CN)(3)]·H(2)O·MeOH [1; Tp*(Bn) = tris(3,5-dimethyl-4-benzyl)pyrazolylborate] with nickel(II) trifluoromethanesulfonate gives {[(Tp*(Bn))Fe(III)(CN)(3)](2)[Ni(II)(DMF)(4)]}·2DMF (2; DMF = N,N-dimethylformamide). The symmetry-equivalent Fe(III)(LS) ions lead to a favorable alignment of anisotropy tensors (i.e., Fe···B axes) in 2, and an energy barrier of Δ(eff)/k(B) = 16.7 K is found for the S(T) = 2 complex.

Spin-state switches in molecular materials chemistry

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