Spin-State Switching and Conductivity in Metal Complexes with Non-Innocent Ligands

具有非无害配体的金属配合物中的自旋态转换和电导率

基本信息

批准号：
1955754
负责人：
Mykhailo Shatruk
金额：
$ 48万
依托单位：
Florida State University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2020
资助国家：
美国
起止时间：
2020-05-01 至 2023-04-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1955754&HistoricalAwards=false
关键词：
Spin State Switching Conductivity Metal

项目摘要

In this project funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, a collaborative research team led by Professor Mykhailo Shatruk of the Department of Chemistry and Biochemistry and Professor Stephen O Hill of the Department of Physics at Florida State University will study stimuli-responsive molecules. These molecules are formed by surrounding transition metal ions by organic groups (ligands) capable of inducing a change in the magnetic state at the metal center. Magnetic state switching in molecular solids is largely unexplored and holds potential to develop into stimuli-responsive materials that could be used in new sensors and catalytic systems. The project will also explore the use of these molecules for the preparation of solids that combine magnetic state switching with electrical conductivity. Such multifunctional materials can be useful for the design of next-generation electronic devices and light-activated switches. The project will provide diverse research experiences to graduate and undergraduate students, including students from groups underrepresented in physical sciences. The outreach efforts include organizing nationwide undergraduate summer schools in magnetism and magnetic resonance spectroscopy.This project targets the synthesis and extensive characterization of spin-state switching materials based on the combination of Fe(II) ions with non-innocent (redox-active) organic ligands. The mechanism of the spin-state transition induced by a reversible electron transfer between an outer-sphere moiety and the coordinated ligand is largely unexplored. Establishing conditions that lead to such spin-state switching phenomena may open a new class of stimuli-responsive molecules, capable of translating temperature-, pressure-, or light-induced outer-sphere electron transfer into dramatic changes in the magnetic and structural states of the system. The team will systematically explore the design and synthesis of such complexes, followed by their detailed characterization by X-ray structural analysis, magnetic property measurements, and various types of magnetic resonance spectroscopy. The behavior of complexes will be studied under various external perturbations to establish the conditions that lead to spin-state switching. These stimuli-responsive molecules will be co-crystallized with anionic organic radicals to obtain hybrid multifunctional materials that combine spin-state switching with electrical conductivity. Changes in the spin configuration at the metal center typically lead to significant atomic displacements that propagate through the entire structure. The possibility to translate such structural perturbations at the magnetically active metal center to the organic substructure and modulate conductivity via spin-state switching is especially appealing if it can be stimulated by light irradiation. Beyond the discovery of a new class of stimuli-responsive complexes and materials, the findings expected from this project will be also of value to the areas of catalysis and bioinorganic chemistry.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

该项目由化学部化学结构、动力学与机理B项目资助，由佛罗里达州立大学化学与生物化学系Mykhailo Shatruk教授和物理系Stephen O Hill教授领导的合作研究小组将研究刺激响应分子。这些分子是由能够引起金属中心磁性状态变化的有机基团（配体）包围过渡金属离子而形成的。分子固体中的磁态转换在很大程度上尚未被探索，并且有潜力发展成可用于新传感器和催化系统的刺激响应材料。该项目还将探索使用这些分子来制备将磁态转换与导电性相结合的固体。这种多功能材料可用于下一代电子设备和光控开关的设计。该项目将为研究生和本科生提供多样化的研究经验，包括来自物理科学领域代表性不足群体的学生。推广工作包括组织全国范围内的磁学和磁共振波谱学本科生暑期学校。该项目的目标是基于 Fe(II) 离子与非无害（氧化还原活性）有机物的结合来合成和广泛表征自旋态转换材料。配体。由外球部分和配位配体之间的可逆电子转移引起的自旋态转变的机制很大程度上尚未被探索。建立导致这种自旋态转换现象的条件可能会开辟一类新的刺激响应分子，能够将温度、压力或光诱导的外层电子转移转化为磁性和结构状态的巨大变化。系统。该团队将系统地探索此类复合物的设计和合成，然后通过X射线结构分析、磁性能测量和各种类型的磁共振波谱对其进行详细表征。将研究配合物在各种外部扰动下的行为，以确定导致自旋态切换的条件。这些刺激响应分子将与阴离子有机自由基共结晶，以获得将自旋态切换与导电性结合起来的杂化多功能材料。金属中心自旋构型的变化通常会导致显着的原子位移，并传播到整个结构。如果可以通过光照射来激发，那么将磁活性金属中心的这种结构扰动转化为有机子结构并通过自旋态转换调节电导率的可能性就特别有吸引力。除了发现一类新的刺激响应复合物和材料之外，该项目的预期结果对于催化和生物无机化学领域也具有价值。该奖项反映了 NSF 的法定使命，并通过评估被认为值得支持利用基金会的智力优势和更广泛的影响审查标准。

项目成果

期刊论文数量（16）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Tuning Magnetic Interactions Between Triphenylene Radicals by Variation of Crystal Packing in Structures with Alkali Metal Counterions

通过改变碱金属抗衡离子结构中的晶体堆积来调节苯并菲自由基之间的磁相互作用

DOI：
10.1021/acs.inorgchem.1c02139
发表时间：
2021-10
期刊：
Inorganic Chemistry
影响因子：
4.6
作者：
Zhou, Zheng;Üngör, Ökten;Wei, Zheng;Shatruk, Michael;Tsybizova, Alexandra;Gershoni;Petrukhina, Marina A.
通讯作者：
Petrukhina, Marina A.

Low-spin 1,1′-diphosphametallocenates of chromium and iron

铬和铁的低自旋 1,1‐二磷茂金属盐

DOI：
10.1039/d0cc06518h
发表时间：
2021-01
期刊：
Chemical Communications
影响因子：
4.9
作者：
Greer, Samuel M.;Üngor, Ökten;Beattie, Ross J.;Kiplinger, Jaqueline L.;Scott, Brian L.;Stein, Benjamin W.;Goodwin, Conrad A.
通讯作者：
Goodwin, Conrad A.

Design and Synthesis of Kekulè and Non-Kekulè Diradicaloids via the Radical Periannulation Strategy: The Power of Seven Clar’s Sextets

通过激进的围环化策略设计和合成凯库勒和非凯库勒双自由基：七个克拉六重奏的力量

DOI：
10.1021/jacs.2c09637
发表时间：
2022-12
期刊：
Journal of the American Chemical Society
影响因子：
15
作者：
Kuriakose, Febin;Commodore, Michael;Hu, Chaowei;Fabiano, Catherine J.;Sen, Debashis;Li, Run R.;Bisht, Shubham;Üngör, Ökten;Lin, Xinsong;Strouse, Geoffrey F.;et al
通讯作者：
et al

Pyridyl-Thioethers as Capping Ligands for the Design of Heteroleptic Fe(II) Complexes with Spin-Crossover Behavior

吡啶基硫醚作为封端配体用于设计具有自旋交叉行为的杂配 Fe(II) 配合物

DOI：
10.3390/magnetochemistry7100134
发表时间：
2021-10
期刊：
Magnetochemistry
影响因子：
2.7
作者：
Üngör, Ökten;Igimbayeva, Dilyara;Dragulescu;Yergeshbayeva, Sandugash;Delgado, Teresa;Greer, Samuel M.;Donalson, Gabrielle;Jo, Minyoung;Erkasov, Rakhmetulla;Shatruk, Michael
通讯作者：
Shatruk, Michael

Optimization of crystal packing in semiconducting spin-crossover materials with fractionally charged TCNQ δ− anions (0 δ < 1)

带有分数电荷 TCNQ δ 阴离子 (0 δ < 1) 的半导体自旋交叉材料中晶体堆积的优化