Garnier D, Jiménez J-R, Li Y, von Bardeleben J, Journaux Y, Augenstein T, Moos E M B, Gamer M T, Breher F, Lescouëzec R
Institute of Inorganic Chemistry , Karlsruhe Institute of Technology (KIT) , Engesserstr. 15, Geb. 30.45 , D-76131 Karlsruhe , Germany . Email:
Institut Parisien de Chimie Moléculaire - CNRS UMR 8232 , UPMC - Paris 6 , Sorbonne Universités , 4 place Jussieu , F-75252 Paris cedex 05 , France . Email:
Chem Sci. 2016 Aug 1;7(8):4825-4831. doi: 10.1039/c6sc01435f. Epub 2016 May 13.
Straightforward access to a new cyanide-bridged {FeCo} "molecular box" containing a potassium ion, namely K⊂{[Fe(Tp)(CN)][Co(Tp)][Co(Tp)]} () (with Tp and Tp = tris- and tetrakis(pyrazolyl)borate, respectively), is provided, alongside its full characterisation. A detailed analysis of the molecular structure (X-ray diffraction, mass spectrometry, NMR spectroscopy) and electronic properties (EPR spectroscopy, SQUID magnetometry, UV/Vis spectroscopy, cyclic voltammetry) reveals that shows slow magnetic relaxation and a remarkable photomagnetic effect at low temperature which is reminiscent of some FeCo Prussian Blue Analogues (PBAs), and is ascribed to a photo-induced electron transfer. However, in contrast with these inorganic polymers, the overall neutral compound is soluble and remarkably stable in organic solvents such as CHCl. Moreover, shows interesting redox versatility, with electrochemical experiments revealing the possible access to six stable redox states.
本文报道了一种新型含钾离子的氰基桥联{FeCo}“分子盒”，即K⊂{[Fe(Tp)(CN)][Co(Tp)][Co(Tp)]} ()（其中Tp和Tp分别为三（吡唑基）硼酸根和四（吡唑基）硼酸根）的简便合成方法及其全面表征。通过对分子结构（X射线衍射、质谱、核磁共振光谱）和电子性质（电子顺磁共振光谱、超导量子干涉仪磁强计、紫外/可见光谱、循环伏安法）的详细分析表明，该化合物在低温下表现出缓慢的磁弛豫和显著的光磁效应，这与一些FeCo普鲁士蓝类似物（PBAs）相似，归因于光诱导电子转移。然而，与这些无机聚合物不同的是，整体呈中性的化合物在诸如CHCl等有机溶剂中可溶且非常稳定。此外，该化合物还表现出有趣的氧化还原多样性，电化学实验表明它可能具有六种稳定的氧化还原状态。
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