Collaborative Research: Surface Coordination Chemistry: Toward Novel Functionality via Understanding Substrate Charge Transfer and Oxidation State

合作研究：表面配位化学：通过了解基底电荷转移和氧化态实现新功能

• 批准号: 1310327
• 负责人: Talat Rahman
• 金额: $ 26.8万
• 依托单位: The University of Central Florida Board of Trustees
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-06-15 至 2017-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1310327&HistoricalAwards=false
• 关键词: Collaborative; Research; Surface; Coordination; Chemistry

In this project, funded by the Macromolecular, Supramolecular and Nanochemistry Program of the Chemistry Division, Prof. Talat S. Rahman of University of Central Florida and Prof. Ludwig Bartels of the University of California, Riverside, and their students will use a combination of scanning tunneling microscopy and first principles electronic structure calculations to image and understand the formation of metal coordination networks on a number of metallic surfaces. They will explore in detail electronic properties of these supported metal coordination centers to address properties such as (i) charge transfer (between molecule & substrate, metal-center & molecule, and metal-center & substrate), and (ii) shape and energetics of molecular orbitals and their relation to conventional metal organic chemistry. Tuning of the effective oxidation state of metal-centers and of ligand HOMO-LUMO gaps by suitable choice of the substrate electronic properties will provide descriptors for variation of the local chemical and geometrical environment. Furthermore, general rules that define the coordination geometry around metal-centers on surfaces will be sought and conditions for stability of coordination centers with specific geometry (e.g., triagonal vs. square) will be tested. Attention will also be paid to understanding the magnetic characteristics of metal coordination centers: metal-center/molecule/substrate combinations which conspire to produce stable magnetic networks will be pursued.This project will provide state of the art modeling and/or laboratory experiences for graduate and undergraduate students and junior scientists who will be learning the techniques of chemical synthesis, formation of metal coordination networks on various metallic surfaces, imaging, and complementary ab initio electronic structure calculations. The project consists of a systematic exploration of coordination chemistry at metal surfaces which will provide the framework for establishing the rules that distinguish it from conventional ligand field and crystal field theory, which govern solution-phase metal organic chemistry. Examination of vibrational and magnetic characteristics of the systems and the special role of dispersion forces will add further value to the proposed work. Through leadership by a theorist, this project is certain to create systematic understanding, deeper insights and faster validation of findings and their generalizations to other systems. The proposed work is expected to have impact on industrial methodologies and society at large by providing access to metal coordination networks in a deterministic fashion. Control of such structures will allow continuous surface patterning from the atomic to the macroscopic scale, which should prove important for a large range of microelectronic, optoelectronic and magnetic applications. The work will also provide opportunities for educational and outreach activities with proven broad national, international and societal impact.

在这个项目中，由化学部的大分子，超分子和纳米化学计划资助，中央佛罗里达大学的塔拉特·S·拉赫曼教授和加利福尼亚大学，河滨大学的路德维希·巴特尔斯教授及其学生将使用扫描隧道微镜和第一原理的组合来形成的图像和组合的组合，以实现扫描隧道的组合，以形成图像的形式，表面。他们将详细探讨这些受支持的金属配位中心的电子性能，以解决（i）电荷转移（分子和底物之间，金属中心和金属和金属中心和中心及底物之间）以及（ii）分子轨道的形状和能量学及其与传统金属有机化学的关系。通过适当选择底物电子性能来调整金属中心和配体均卢莫缝隙的有效氧化状态，将为局部化学和几何环境的变化提供描述。此外，将寻求定义表面上金属中心围绕的配位几何形状的一般规则，并将测试具有特定几何形状的协调中心稳定性的条件（例如，Triagonal vs. Square）。 Attention will also be paid to understanding the magnetic characteristics of metal coordination centers: metal-center/molecule/substrate combinations which conspire to produce stable magnetic networks will be pursued.This project will provide state of the art modeling and/or laboratory experiences for graduate and undergraduate students and junior scientists who will be learning the techniques of chemical synthesis, formation of metal coordination networks on various metallic surfaces, imaging, and互补的从头算电子结构计算。该项目由对金属表面上的配位化学的系统探索组成，该探索将为建立将其与传统配体场和晶体场理论区分开的规则提供框架，该规则管理溶液相金属有机化学。检查系统的振动和磁性特征以及分散力的特殊作用将为拟议的工作增加进一步的价值。通过理论家的领导，该项目肯定会创造系统的理解，更深入的见解和更快的发现及其对其他系统的概括。预计拟议的工作将通过确定性的方式提供获得金属协调网络的访问，从而对工业方法论和整个社会产生影响。对这种结构的控制将允许从原子到宏观尺度的连续表面图案，这对于大量的微电源，光电和磁性应用来说应该很重要。这项工作还将为教育和外展活动提供机会，并具有广泛的国家，国际和社会影响。