Liu Xue, Zhou Jian, Bao Xin, Yan Zheng, Peng Guo, Rouzières Mathieu, Mathonière Corine, Liu Jun-Liang, Clérac Rodolphe
School of Chemical Engineering, Nanjing University of Science and Technology , 210094 Nanjing, P. R. China.
Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University , Guangdong 515063, P. R. China.
Inorg Chem. 2017 Oct 16;56(20):12148-12157. doi: 10.1021/acs.inorgchem.7b01430. Epub 2017 Sep 22.
Two new mononuclear Fe(II) complexes, [Fe(L)(NCX)] (L = N,N'-dimethyl-N,N'-bis((pyrazin-2-yl)methyl)-1,2-ethanediamine and X = S (1), BH (2)), have been synthesized and characterized by single-crystal X-ray diffraction, magnetic, optical reflectivity, and photomagnetic measurements. They have similar FeN coordination environments offered by the tetradentate ligand with a cis-α conformation and two NCX coligands in cis positions. However, 1 and 2 have different molecular arrangements and crystal packings, and are isolated in orthorhombic Pbnb and monoclinic C2/c space groups, respectively. 1 remains in a high spin state (S = 2) over all temperatures while 2 undergoes a spin transition around 168 K with a small thermal hysteresis of about 0.4 K (at a temperature scan rate of 1.3 K min). This phase transition, which can also be optically detected due to the associated marked change of the sample color, occurs between two structurally characterized phases, which exhibit Fe(II) complexes in their high spin and low spin states at high and low temperatures, respectively. The reversible photoswitching between these two states has also been confirmed at low temperatures using well separated wavelength irradiations.
