Temperature dependence of spherical electron transfer in a nanosized [Fe14] complex

The study of transition metal clusters exhibiting fast electron hopping or delocalization 34 remains challenging, because intermetallic communications mediated through bridging 35 ligands are normally weak. Herein, we report the synthesis of a nanosized complex, 36 [Fe(Tp)(CN)3]8[Fe(H2O)(DMSO)]6 (abbreviated as [Fe14], Tp−, hydrotris(pyrazolyl)borate; 37 DMSO, dimethyl sulfoxide), which has a fluctuating valence due to two mobile d-electrons in 38 its atomic layer shell. The rate of electron transfer of [Fe14] complex demonstrates the 39 Arrhenius-type temperature dependence in the nanosized spheric surface, wherein high-spin centers are ferromagnetically coupled, producing an S = 14 ground state. The electron hopping rate at room temperature is faster than the time scale of Mössbauer measurements (<~10−8 s). Partial reduction of N-terminal high spin FeIII sites and electron mediation ability of CN ligands lead to the observation of both an extensive electron transfer and magnetic coupling properties in a precisely atomic layered shell structure of a nanosized [Fe14] complex.