Probing bistability in Fe(II) and Co(II) complexes with an unsymmetrically substituted quinonoid ligand.

Probing bistability in Fe(II) and Co(II) complexes with an unsymmetrically substituted quinonoid ligand.
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探测具有不对称取代醌配体的 Fe(II) 和 Co(II) 配合物的双稳定性

DOI:
10.1039/c6dt00757k
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发表时间:
2016
影响因子:
4
通讯作者:
B. Sarkar
B. Sarkar
中科院分区:
化学2区
文献类型:
--
作者:
M. van der Meer;Y. Rechkemmer;F. Breitgoff;S. Dechert;R. Marx;M. Dörfel;P. Neugebauer;J. van Slageren;B. Sarkar

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分子平台的性质可以受到各种外部扰动的影响,其生成是功能分子材料领域的一个重要目标。本文合成了一种含有[O,O,O,N]给体的新型醌类配体平台。该配体是用[NR](带取代基R的氮原子)代替[O]等电子取代从氯苯酸核中得到的。用这种新配体合成了单核FeII和CoII配合物。利用单晶x射线晶体学、核磁共振光谱、(谱)电化学、SQUID磁强计、多频EPR光谱和FIR光谱分析了配合物的电子结构和几何结构。此外,我们在这里证明了FeII配合物的自旋状态可以受到温度、压力和光的影响,并且CoII配合物显示氧化还原诱导的自旋状态切换。FeII配合物在固态和溶液中均具有双稳性。与[O,O,O,O]类似物相比,本文提出的新配体由于含有[NR]基团,在研究开关现象时可能具有更强的适应性。因此,这类配体以及所获得的金属配合物物理性质可逆变化的结果很可能有助于多功能分子材料的产生。
The generation of molecular platforms, the properties of which can be influenced by a variety of external perturbations, is an important goal in the field of functional molecular materials. We present here the synthesis of a new quinonoid ligand platform containing an [O,O,O,N] donor set. The ligand is derived from a chloranilic acid core by using the [NR] (nitrogen atom with a substituent R) for [O] isoelectronic substitution. Mononuclear FeII and CoII complexes have been synthesized with this new ligand. Results obtained from single crystal X-ray crystallography, NMR spectroscopy, (spectro)electrochemistry, SQUID magnetometry, multi-frequency EPR spectroscopy and FIR spectroscopy are used to elucidate the electronic and geometric structures of the complexes. Furthermore, we show here that the spin state of the FeII complex can be influenced by temperature, pressure and light and the CoII complex displays redox-induced spin-state switching. Bistability is observed in the solid-state as well as in solution for the FeII complex. The new ligand presented here, owing to the [NR] group present in it, will likely have more adaptability while investigating switching phenomena compared to its [O,O,O,O] analogues. Thus, such classes of ligands as well as the results obtained on the reversible changes in physical properties of the metal complexes are likely to contribute to the generation of multifunctional molecular materials.
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