Optical and Magnetic Molecular Switches Based on Metal-to-Metal Electron Transfer Mechanism: from Solid State to Solution
讲座名称：
Optical and Magnetic Molecular Switches Based on Metal-to-Metal Electron Transfer Mechanism: from Solid State to Solution
讲座时间：
2017-12-06
讲座人：
Rodolphe Clerac
形式：
校区：
兴庆校区
实践学分：
讲座内容：
讲座名称:Optical and Magnetic Molecular Switches Based on Metal-to-Metal Electron Transfer Mechanism: from Solid State to Solution
讲座时间:2017年12月6日，上午10：00
讲座地点:西二楼A102，曲江校区
讲座人:Rodolphe Clérac 教授(法国国家科学研究院帕斯卡研究中心担任主任研究员)
讲座内容:The design of molecule-based systems displaying tunable optical and/or magnetic properties under external stimuli received a great deal of attention in the past few years. This interest is driven by the potential applications in high-performance molecule-based electronics. As an example, 3D Fe/Co Prussian blue compounds exhibit a concomitant change in magnetic and optical properties due to a temperature- or light-induced metal-to-metal electron transfer (ET). The foregoing remarkable properties in Prussian blues prompted us to design soluble molecular fragments of these coordination networks through a rational building-block approach in order to mimic their properties on a single molecule (See Figure). With a judicious choice of the ligands for metal ion precursors, we prepared a octanuclear, tetranuclear and recently dinuclear cyanido-bridged Fe/Co complexes. In the solid state, while an intramolecular ET is observed for the [Co4Fe4] and [Co2Fe2] complexes, the Co ion of our first dinuclear complex exhibits a spin crossover (SCO) involving a [FeIIILS-CN-CoIILS] ground state and a thermally populated [FeIIILS-CN-CoIIHS] state. To our knowledge, this compound is the only example of a heterobimetallic complex exhibiting a CoII SCO. Remarkably, our studies of these [ConFen] complexes in solution reveal important optical and magnetic changes induced by an intramolecular metal-to- metal ET triggered and modulated by a controlled protonation of the complex, by the solvent nature or by temperature. Therefore, these molecules act as different molecular switches depending on their physical state and external stimuli. These results motivated us to design new dinuclear [FeCo] complexes exhibiting both thermally and light induced electron transfer in solid state. Learning from these previous systems, new dinuclear complexes have been designed by a rational building-block approach. Combined structural, spectroscopic, magnetic and photomagnetic studies reveal that a metal-to-metal electron transfer that can be triggered by light, temperature and lattice contents is observed for the first time in solid state for a dinuclear cyanido- bridged Fe/Co complex.
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