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

• 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

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.

在这个由化学部化学结构，动力学机制B计划资助的项目中，由化学和生物化学系的Mykhailo Shatruk教授和佛罗里达州立大学物理系的Stephen O Hill教授领导的合作研究小组将研究刺激响应分子。 这些分子通过用能够引起金属中心处的磁性状态变化的有机基团（配体）包围过渡金属离子而形成。 分子固体中的磁性状态转换在很大程度上尚未探索，并有可能发展成为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联合收割机磁状态切换与导电性结合在一起的固体。这种多功能材料可用于下一代电子器件和光激活开关的设计。该项目将为研究生和本科生提供多样化的研究经验，包括来自物理科学代表性不足的群体的学生。该项目的目标是合成和广泛表征基于Fe（II）离子与非无害（氧化还原活性）有机配体结合的自旋态转换材料。由外层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在很大程度上是未探索的。建立导致这种自旋状态转换现象的条件可能会打开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系统的磁性和结构状态的急剧变化。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，磁特性测量和各种类型的磁共振光谱对其进行详细表征。复合物的行为将在各种外部扰动下进行研究，以建立导致自旋状态切换的条件。这些刺激响应分子将与阴离子有机自由基共结晶，以获得将联合收割机自旋状态转换与导电性结合的杂化多功能材料。在金属中心的自旋配置的变化通常会导致通过整个结构传播的显着的原子位移。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状态切换来调制电导率的可能性特别有吸引力，如果它可以通过光照射来刺激的话。除了发现一类新的刺激响应复合物和材料之外，该项目的预期发现还将对催化和生物无机化学领域具有价值。该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的知识价值和更广泛的影响审查标准进行评估来支持。

项目成果

Investigating reactivity and electronic structure of copper(II)-polypyridyl complexes and hydrogen peroxide

研究铜(II)-聚吡啶配合物和过氧化氢的反应活性和电子结构

• DOI: 10.1016/j.ica.2020.120168
• 发表时间: 2021
• 期刊: Inorganica Chimica Acta
• 影响因子: 2.8
• 作者: Khazanov, Thomas M.;Botcha, Niharika Krishna;Yergeshbayeva, Sandugash;Shatruk, Michael;Mukherjee, Anusree
• 通讯作者: Mukherjee, Anusree

Bimolecular Reductive Elimination of Ethane from Pyridine(diimine) Iron Methyl Complexes: Mechanism, Electronic Structure, and Entry into [2+2] Cycloaddition Catalysis

吡啶（二亚胺）甲基铁配合物双分子还原消除乙烷：机理、电子结构和进入[2 2]环加成催化

• DOI: 10.1021/jacs.2c10547
• 发表时间: 2023
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Kovel, Carli B.;Darmon, Jonathan M.;Stieber, S. Chantal;Pombar, Gisselle;Pabst, Tyler P.;Theis, Bastian;Turner, Zoë R.;Üngör, Ökten;Shatruk, Michael;DeBeer, Serena
• 通讯作者: DeBeer, Serena

Solvent‐Dependent Spin‐Crossover Behavior in Semiconducting Co–Crystals of [Fe(1‐bpp) 2 ] 2+ Cations and TCNQ δ− Anions (0

溶剂 — 相关自旋 — [Fe(1 — bpp) 2 ] 2 阳离子和 TCNQ 阴离子 (0

• DOI: 10.1002/ejic.202100707
• 发表时间: 2021
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: Üngör, Ökten;Choi, Eun Sang;Shatruk, Michael
• 通讯作者: Shatruk, Michael

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
• 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.

Abrupt Spin Transition in a Heteroleptic Fe(II) Complex with Pendant Naphthalene Functionality

具有侧萘官能团的杂配 Fe(II) 配合物中的突变自旋跃迁

• DOI: 10.1021/acs.inorgchem.2c01490
• 发表时间: 2022
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Yergeshbayeva, Sandugash;Hrudka, Jeremy J.;Jo, Minyoung;Gakiya-Teruya, Miguel;Meisel, Mark W.;Shatruk, Michael
• 通讯作者: Shatruk, Michael