Chemical, Electrochemical and Physical Properties of Metallosupramolecular Architectures with Neutral and Radical Bridging Ligands and the Influence of Non-Covalent Interactions
具有中性和自由基桥连配体的金属超分子结构的化学、电化学和物理性质以及非共价相互作用的影响
基本信息
- 批准号:1808779
- 负责人:
- 金额:$ 64万
- 依托单位:
- 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:2018-08-01 至 2023-07-31
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
From common refrigerator magnets to tiny magnetic particles on which data are recorded in hard drives, magnets are pervasive in everyday life. The reduction in size of magnetic particles over the past several decades has led to significant increase in the storage capacity but the limit is being reached. Professor Dunbar's group at Texas A&M University Main Campus explores new types of chemical structures that display magnetic behavior at the nanoscale level. Through systematic investigation of the structure-property relationships of these magnetic compounds, the team aims to gain a better fundamental understanding of the factors that contribute to superior magnetic properties and provide insight to inform design of the next generation magnets for computing or electronic storage devices. The versatility of skills required to work on this project is an excellent opportunity for students, including members of underrepresented groups, to learn chemical synthesis as well as numerous methods of characterization. The Macromolecular, Supramolecular and Nanochemistry Program of the NSF Chemistry Division supports Prof. Dunbar's group to synthesize and study the properties of multinuclear transition and lanthanide metal supramolecular architectures with neutral and radical bridging ligands. Whereas more commonly used closed-shell (diamagnetic) bridging ligands engage in superexchange (indirect) interactions between the metal spins, radical bridging ligands facilitate direct exchange interactions which results in much stronger magnetic coupling. For transition metal complexes, this situation results in modest coupling and in lanthanide complexes these interactions are very weak. Magnetic coupling in both transition metal complexes and lanthanide rare earth complexes is greatly improved by using a radical bridging ligand that can engage in direct exchange with the metal ions. In order to further improve upon these systems, the Dunbar group seeks to generate new classes of radical-bridged magnetic complexes using supramolecular strategies. This project focuses on using N-heterocyclic neutral ligands that feature interactions between anions and electron deficient aromatic rings, namely the anion-pi interaction. The neutral ligand can undergo a reversible one-electron reduction at accessible potentials to form a stable radical. Computatonal studies are performed to identify the most synthetically feasible targets and guide the direction of research as it progresses. Spontaneous self-assembly of paramagnetic metal ions with the ligands gives multinuclear supramolecular complexes in high yields due to anion and solvent templates. A plethora of techniques (including single-crystal X-ray crystallography, SQUID magnetometry, electrochemistry, and electron paramagnetic resonance) is used to study the rich electronic, redox, and magnetic properties of these supramolecular architectures. By comparing the properties of the complexes with a variety of ligands with different electron donating ability and coordinating geometry, this research aims to unveil the structural and electronic factors that contribute to superior magnetic coupling.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.
从普通的冰箱磁铁到将数据记录在硬盘驱动器上的微小磁性颗粒,磁铁在日常生活中无处不在。在过去的几十年里,磁性颗粒的尺寸减小导致了存储容量的显着增加,但正在达到极限。德州农工大学主校区的邓巴教授的团队探索了在纳米尺度上显示磁性行为的新型化学结构。通过系统地研究这些磁性化合物的结构-性能关系,该团队旨在更好地从根本上了解导致优异磁性的因素,并为设计用于计算或电子存储设备的下一代磁体提供洞察力。从事这一项目所需的多才多艺的技能是学生,包括代表人数不足的群体的成员,学习化学合成以及各种表征方法的绝佳机会。NSF化学部的大分子、超分子和纳米化学计划支持Dunbar教授的团队合成和研究具有中性和自由基桥联配体的多核过渡金属和稀土金属超分子结构的性质。虽然更常用的闭壳(抗磁性)桥联配体参与金属自旋之间的超交换(间接)相互作用,但自由基桥联配体促进直接交换相互作用,从而导致更强的磁耦合。对于过渡金属络合物,这种情况导致适度的耦合,而在稀土络合物中,这些相互作用非常弱。通过使用能与金属离子直接交换的自由基桥联配体,大大改善了过渡金属络合物和稀土稀土络合物中的磁性耦合。为了进一步改进这些体系,Dunbar小组寻求使用超分子策略来生成新的自由基桥接磁性络合物。本项目的重点是使用N-杂环中性配体,其特征是阴离子与缺电子芳香环之间的相互作用,即阴离子-pi相互作用。中性配体可以在接近的电位下进行可逆单电子还原,形成稳定的自由基。进行计算机研究是为了确定最综合可行的目标,并在其进展过程中指导研究方向。由于阴离子和溶剂模板的存在,顺磁性金属离子与配体的自发自组装形成了高产率的多核超分子络合物。大量的技术(包括单晶X射线结晶学、SQUID磁学、电化学和电子顺磁共振)被用来研究这些超分子结构的丰富的电子、氧化还原和磁性。通过比较具有不同电子给体能力和配位几何构型的各种配体的络合物的性质,这项研究旨在揭示促成优异磁耦合的结构和电子因素。这一奖项反映了NSF的法定使命,并通过使用基金会的智力优势和更广泛的影响审查标准进行评估,被认为值得支持。
项目成果
期刊论文数量(20)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
A Co8 metallacycle stabilized by double anion-π interactions
- DOI:10.1039/c9cc04151f
- 发表时间:2019-10-21
- 期刊:
- 影响因子:4.9
- 作者:Alexandropoulos, Dimitris, I;Dolinar, Brian S.;Dunbar, Kim R.
- 通讯作者:Dunbar, Kim R.
Hexagonal Bipyramidal Dy(III) Complexes as a Structural Archetype for Single-Molecule Magnets
六方双锥 Dy(III) 配合物作为单分子磁体的结构原型
- DOI:10.1021/acs.inorgchem.8b03206
- 发表时间:2019
- 期刊:
- 影响因子:4.6
- 作者:Li Jing;Gomez Coca Silvia;Dolinar Brian S;Yan Li;Yu Fei;Kong Ming;Zhang Yi Quan;Song You;Dunbar Kim R
- 通讯作者:Dunbar Kim R
Quinoxaline radical-bridged transition metal complexes with very strong antiferromagnetic coupling
具有极强反铁磁耦合的喹喔啉自由基桥接过渡金属配合物
- DOI:10.1039/d0cc03713c
- 发表时间:2020
- 期刊:
- 影响因子:4.9
- 作者:Alexandropoulos, Dimitris I.;Vignesh, Kuduva R.;Xie, Haomiao;Dunbar, Kim R.
- 通讯作者:Dunbar, Kim R.
Synthesis and magnetic studies of pentagonal bipyramidal metal complexes of Fe, Co and Ni
Fe、Co 和 Ni 五角双锥体金属配合物的合成和磁性研究
- DOI:10.1039/c8dt05074k
- 发表时间:2019-03-14
- 期刊:
- 影响因子:4
- 作者:Deng, Yi-Fei;Yao, Binling;Dunbar, Kim R.
- 通讯作者:Dunbar, Kim R.
Probing the Axial Distortion Effect on the Magnetic Anisotropy of Octahedral Co(II) Complexes
探讨轴向畸变对八面体 Co(II) 配合物磁各向异性的影响
- DOI:10.1021/acs.inorgchem.0c00531
- 发表时间:2020-06-01
- 期刊:
- 影响因子:4.6
- 作者:Deng, Yi-Fei;Singh, Mukesh Kumar;Dunbar, Kim R.
- 通讯作者:Dunbar, Kim R.
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Kim Dunbar其他文献
Kim Dunbar的其他文献
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{{ truncateString('Kim Dunbar', 18)}}的其他基金
Chemical, Electrochemical and Physical Properties of Metallosupramolecular Architectures with Tetrazine Based Ligands Including Investigations of Anion-pi Interactions
具有四嗪基配体的金属超分子结构的化学、电化学和物理性质,包括阴离子-pi 相互作用的研究
- 批准号:
1310574 - 财政年份:2013
- 资助金额:
$ 64万 - 项目类别:
Continuing Grant
Magnetism, Conductivity and the Interplay between these Properties in d, p and f block Materials with Organocyanide Ligands
d、p 和 f 嵌段材料与有机氰化物配体的磁性、电导率以及这些特性之间的相互作用
- 批准号:
0957840 - 财政年份:2010
- 资助金额:
$ 64万 - 项目类别:
Continuing Grant
Systematic Studies of the Structural, Magnetic, and Spectroscopic Properties of Clusters and Extended Arrays Based on Cyanide Ligands
基于氰化物配体的团簇和扩展阵列的结构、磁性和光谱性质的系统研究
- 批准号:
0610019 - 财政年份:2006
- 资助金额:
$ 64万 - 项目类别:
Continuing Grant
Molecules, Large Clusters and Extended Arrays with Open-Shell Metal-Ligand Units: Syntheses, Magento-Structural Correlations and Applications to Materials Design
具有开壳金属配体单元的分子、大簇和扩展阵列:合成、Magento 结构相关性及其在材料设计中的应用
- 批准号:
9906583 - 财政年份:1999
- 资助金额:
$ 64万 - 项目类别:
Standard Grant
Ordered Arrays of Metals with Polynitrile or Cyanide Ligands
具有聚腈或氰化物配体的有序金属阵列
- 批准号:
9622589 - 财政年份:1996
- 资助金额:
$ 64万 - 项目类别:
Standard Grant
U.S.-France Cooperative Research: Synthetic Strategies, Structural Aspects and Cooperative Behavior of Charge- Transfer Compounds.
美法合作研究:电荷转移化合物的合成策略、结构方面和合作行为。
- 批准号:
9217191 - 财政年份:1993
- 资助金额:
$ 64万 - 项目类别:
Standard Grant
New Transition Metal Complexes and Low Dimensional Compoundswith Nitrile, Cyanide or Phosphine Ligands
具有腈、氰化物或膦配体的新型过渡金属配合物和低维化合物
- 批准号:
9311812 - 财政年份:1993
- 资助金额:
$ 64万 - 项目类别:
Standard Grant
Coordination Chemistry of Reactive Homoleptic Acetonitrile Complexes with an Unusual Bulky Alkoxo-Phosphine Ligand
反应性均配乙腈配合物与异常大的烷氧膦配体的配位化学
- 批准号:
8914915 - 财政年份:1990
- 资助金额:
$ 64万 - 项目类别:
Continuing Grant
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Fine tuning of structural and physical properties of transition metal halides by electrochemical intercalation
通过电化学插层微调过渡金属卤化物的结构和物理性质
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2326843 - 财政年份:2023
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CAREER: Understanding the electrochemical properties of physical hole defects on functionalized B/C 2D materials for the 2e- reduction of O2 to H2O2
职业:了解功能化 B/C 2D 材料上物理孔缺陷的电化学特性,用于将 O2 2e 还原为 H2O2
- 批准号:
2048278 - 财政年份:2021
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Mass transfer prediction model in unsaturated concrete based on electrochemical physical properties
基于电化学物理性质的非饱和混凝土传质预测模型
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19K04545 - 财政年份:2019
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$ 64万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Physical and Electrochemical Improvement of Alloy-Containing Electrodes
含合金电极的物理和电化学改进
- 批准号:
510506-2017 - 财政年份:2017
- 资助金额:
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Experience Awards (previously Industrial Undergraduate Student Research Awards)
Chemical, Electrochemical and Physical Properties of Metallosupramolecular Architectures with Tetrazine Based Ligands Including Investigations of Anion-pi Interactions
具有四嗪基配体的金属超分子结构的化学、电化学和物理性质,包括阴离子-pi 相互作用的研究
- 批准号:
1310574 - 财政年份:2013
- 资助金额:
$ 64万 - 项目类别:
Continuing Grant
Ellucidation of the Physical and Chemical Changes on the Surface of Electrochemical Biosensors for the Detection and Quantification of Hormones
阐明用于激素检测和定量的电化学生物传感器表面的物理和化学变化
- 批准号:
391453-2010 - 财政年份:2012
- 资助金额:
$ 64万 - 项目类别:
Vanier Canada Graduate Scholarships - Doctoral
Precision control of physical properties of topological insulators/superconductors by electrochemical method
电化学方法精确控制拓扑绝缘体/超导体的物理性质
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24540320 - 财政年份:2012
- 资助金额:
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Ellucidation of the Physical and Chemical Changes on the Surface of Electrochemical Biosensors for the Detection and Quantification of Hormones
阐明用于激素检测和定量的电化学生物传感器表面的物理和化学变化
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- 资助金额:
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Ellucidation of the Physical and Chemical Changes on the Surface of Electrochemical Biosensors for the Detection and Quantification of Hormones
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