Chemical Triggers for Spin-State Switching: Discovery and Control of Switching Mechanisms

自旋态转换的化学触发：转换机制的发现和控制

• 批准号: 1800554
• 负责人: Matthew Shores
• 金额: $ 14万
• 依托单位: Colorado State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-01 至 2019-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800554&HistoricalAwards=false
• 关键词: Chemical; Triggers; Spin; State; Switching

In this project, funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Matthew Shores of the Department of Chemistry at Colorado State University (CSU) is exploring new classes of transition metal complexes that can serve as molecular switches. The goal of the research is to understand how host-guest interactions alter the structure of coordination complexes and change their magnetic properties. These results will inform design principles for the development of chemical sensors, switchable molecular magnets, and magnetic resonance contrast agents. The project combines several synthetic, measurement and computational techniques to provide diverse training for the research students involved. Interactions with the CSU Chemistry Research Experiences for Undergraduates program and collaborations with researchers at CSU-Pueblo aim to broaden participation from underrepresented groups. The group's expertise in magnetic measurements and data interpretation will promote discovery via several ongoing and new magnetic collaborations with inorganic and materials chemistry research groups around the country.Complexes that can exist in and reliably switch between two well-defined magnetic states offer the possibility for functional materials development at the nano- and molecular length scales. The proposed research aims to enhance magnetic property switching in transition metal complexes by controlling local geometry and ligand field effects via outer sphere, non-covalent interactions with guest molecules. Specific research goals for this project are: (1) computational understanding of thermodynamics and distortion pathways in magnetic-state switching, toward predictive models; (2) exploration of new chemical triggers and new ions for guest-dependent spin-state switching complexes; and (3) external control of axial magnetic anisotropy in Co(II) single-molecule magnet complexes. The ultimate aim is to gain new understanding in the design of novel mechanisms for magnetic property switching, and contribute new sensing architectures relevant to chemical sensing and molecular imaging applications.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.

在这个项目中，由化学系的化学结构，动力学机制B计划资助，科罗拉多州立大学（CSU）化学系的Matthew Shores教授正在探索可以作为分子开关的过渡金属络合物的新类别。该研究的目标是了解主客体相互作用如何改变配位复合物的结构并改变其磁性。这些结果将为化学传感器、可切换分子磁体和磁共振造影剂的开发提供设计原则。该项目结合了几种合成，测量和计算技术，为参与研究的学生提供多样化的培训。与CSU本科生化学研究经验计划的互动以及与CSU普韦布洛研究人员的合作旨在扩大代表性不足群体的参与。该团队在磁性测量和数据解释方面的专业知识将通过与全国各地的无机和材料化学研究小组进行的几项正在进行的和新的磁性合作来促进发现。可以存在于两种明确定义的磁性状态并在两种明确定义的磁性状态之间可靠切换的复合物为纳米和分子尺度的功能材料开发提供了可能性。该研究旨在通过控制局部几何形状和配体场效应，通过与客体分子的非共价相互作用，增强过渡金属配合物的磁性切换。该项目的具体研究目标是：（1）计算理解磁态转换中的热力学和畸变途径，走向预测模型;（2）探索新的化学触发剂和新离子，用于客体依赖的自旋态转换复合物;（3）Co（II）单分子磁体复合物中轴向磁各向异性的外部控制。该奖项的最终目的是获得新的理解，在新的机制设计的磁性开关，并有助于新的传感架构相关的化学传感和分子成像应用。该奖项反映了NSF的法定使命，并已被认为是值得的支持，通过评估使用基金会的知识价值和更广泛的影响审查标准。

项目成果

Evidence for Reagent-Induced Spin-State Switching in Tripodal Fe(II) Iminopyridine Complexes

三足 Fe(II) 亚氨基吡啶配合物中试剂诱导自旋态转换的证据

• DOI: 10.1021/acs.inorgchem.9b00340
• 发表时间: 2019
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Ozumerzifon, Tarik J.;Higgins, Robert F.;Joyce, Justin P.;Kolanowski, Jacek L.;Rappé, Anthony K.;Shores, Matthew P.
• 通讯作者: Shores, Matthew P.

Magnetization Slow Dynamics in Ferrocenium Complexes

• DOI: 10.1002/chem.201900799
• 发表时间: 2019-07-17
• 期刊: CHEMISTRY-A EUROPEAN JOURNAL
• 影响因子: 4.3
• 作者: Ding, Mei;Hickey, Anne K.;Smith, Jeremy M.
• 通讯作者: Smith, Jeremy M.

Excited-state effects on magnetic properties of U( iii ) and U( iv ) pyrazolylborate complexes

激发态对 U( iii ) 和 U( iv ) 吡唑基硼酸盐配合物磁性能的影响

• DOI: 10.1039/c9cc04800f
• 发表时间: 2019
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Higgins, Robert F.;Tatebe, Caleb J.;Bart, Suzanne C.;Shores, Matthew P.
• 通讯作者: Shores, Matthew P.

Heterobimetallic {PtMn} and {PtFe} lantern complexes with exceptionally long metallophilic contacts

• DOI: 10.1016/j.ica.2019.04.054
• 发表时间: 2019-07-01
• 期刊: INORGANICA CHIMICA ACTA
• 影响因子: 2.8
• 作者: Beach, Stephanie A.;Zuckerman, Linda A.;Doerrer, Linda H.
• 通讯作者: Doerrer, Linda H.

Investigation of the Electronic Structure of Aryl-Bridged Dinuclear U(III) and U(IV) Compounds

芳基桥双核 U(III) 和 U(IV) 化合物的电子结构研究

• DOI: 10.1021/acs.organomet.8b00794
• 发表时间: 2019
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Tatebe, Caleb J.;Kiernicki, John J.;Higgins, Robert F.;Ward, Robert J.;Natoli, Sean N.;Langford, James C.;Clark, Christopher L.;Zeller, Matthias;Wenthold, Paul;Shores, Matthew P.
• 通讯作者: Shores, Matthew P.