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
讲座地点 西二楼A102,曲江校区
讲座人 Rodolphe Clerac
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.

 

讲座人介绍

鲁道夫•克莱拉克(Rodolphe Clérac)教授被称为“单链磁体之父”,是近5年法国化学家中发表科学研究论文最多的学者(158篇)。Clérac教授出生于1971年,1997年获得法国波尔多第一大学物理化学博士学位。曾任波尔多第一大学暨帕斯卡研究中心副教授,现在法国国家科学研究院帕斯卡研究中心担任主任研究员。Rodolphe Clérac教授主要研究领域包括功能分子材料、单链磁体和新型分子磁性材料,在理解和分析分子基材料的物理性能方面的杰出能力蜚声国际,与全球20多个国家的60多个研究小组与其合作。Clérac教授应邀在世界各地讲学76次;目前已发表论文424篇,包括Nature子刊、JACS、ACIE、PRL等高水平杂志,被引用15739次, H-指数达67。他同时也是英国皇家化学会、美国化学会、法国化学会等杰出会员。2009年获得法国化学物理部青年学者奖,2009-2012年度及2013-2016年度法国国家卓越科学奖。

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