Synthesis and Properties of Photomagnetic Molecular Switches based on Spin Crossover Iron(II) Complexes Featuring Photoisomerizable Ligands

基于光异构配体自旋交叉铁(II)配合物的光磁分子开关的合成与性能

• 批准号: 255181289
• 负责人: Privatdozent Dr. Marat Khusniyarov
• 金额: --
• 依托单位: Lehrstuhl für Anorganische und Allgemeine Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2014
• 资助国家: 德国
• 起止时间: 2013-12-31 至 2017-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/255181289?language=en
• 关键词: Synthesis; Properties; Photomagnetic; Molecular; Switches

Spin crossover (SCO) metal complexes are among the best known classes of molecular bistable systems which magnetic properties can be reversibly switched by changing temperature, applied pressure, electric and magnetic field, or irradiation with light. The most common SCO species are iron(II) complexes that offer a brilliant opportunity to switch between a diamagnetic low-spin and paramagnetic high-spin states via external stimuli. Controlling a molecule's state via light irradiation is very attractive due to the extraordinary high speed of switching, easy and precise addressing and high selectivity that suggests application of SCO complexes as photoswitchable building blocks for molecular electronics and spintronics, communication networks, ultra-high density memories, and others. Recently we developed a unique molecular switch 1 - a SCO iron(II) complex featuring a photoactive diarylethene derived ligand L. The integration of the photoisomerizable ligand L into the SCO species 1 allowed us to switch reversibly magnetic properties with moderate efficiency with light at room temperature (RT). In the present work we will chemically modify the ligand L and synthesize corresponding SCO iron(II) complexes. The proposed chemical modifications of L pursue the following goals: 1) to improve the photophysical properties of molecular switches based on 1, 2) to increase the thermal stability of the switches, 3) to increase a photomagnetic effect at RT, 4) to allow the grafting of molecular switches to the gold surface. Thus, a whole family of molecular switches based on the parent complex 1 will be synthesized and their photomagnetic properties will be investigated in solution and in the solid state. Initial experiments on grafting of molecular switches to the gold surface and investigation of their photomagnetic properties at the surface will be performed. The results obtained on this project may open a great opportunity to switch efficiently and reversibly magnetic properties of molecules in thin films and single molecules with light at RT that could find diverse applications in molecular electronics and spintronics at RT.

自旋跨界（SCO）金属络合物是最著名的分子双轴系统类别之一，可以通过变化的温度，施加的压力，电场和磁场或光照射来可逆地切换磁性特性。最常见的SCO物种是铁（II）复合物，它们通过外部刺激为切换二磁性低自旋和顺磁性高旋转状态提供了绝佳的机会。通过光照射控制分子状态非常有吸引力，这是因为开关的高速，易于且精确的地址和高选择性，这表明将SCO复合物用作分子电子和自旋型的可相互作用构建块，通信网络，超高密度记忆以及其他分子的构建块。最近，我们开发了一种独特的分子开关1- SCO铁（II）复合物，具有光活性二二乙烯衍生的配体L。将光异构体的配体L整合到SCO物种中1使我们能够以室温（RT）的光效率为中等效率的中等磁性切换，并在室温下（RT）切换磁性特性。在目前的工作中，我们将化学修改配体L并合成相应的SCO铁（II）配合物。提出的L l追求以下目标的化学修饰：1）基于1，2）提高分子开关的光物理特性，以提高开关的热稳定性，3）3）增加了RT时的光磁效应，4）以允许将分子开关的抓地力植根于金表面。因此，将合成基于父络合物1的整个分子开关，并将在溶液和固态中研究其光磁特性。将对分子开关移植到金表面的最初实验，并研究其表面的光磁特性。该项目获得的结果可能为在RT处有光线和单分子中有效和可逆的分子的磁性开辟了一个绝佳的机会，可以在RT上找到分子电子和Spintronics中的不同应用。

项目成果

Synthesis, Characterization, and Properties of Iron(II) Spin-Crossover Molecular Photoswitches Functioning at Room Temperature.

• DOI: 10.1021/acs.inorgchem.7b01952
• 发表时间: 2017-10
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: Max Mörtel;Alexander Witt;F. Heinemann;S. Bochmann;J. Bachmann;Marat M. Khusniyarov

Room temperature control of spin states in a thin film of a photochromic iron(II) complex

• DOI: 10.1039/c7mh01042g
• 发表时间: 2018-05
• 期刊: Materials horizons
• 影响因子: 13.3
• 作者: Lorenzo Poggini;M. Milek;G. Londi;A. Naim;G. Poneti;L. Squillantini;A. Magnani;F. Totti;P. Rosa;Marat M. Khusniyarov;M. Mannini