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.

在这个由化学系高分子、超分子和纳米化学项目资助的项目中，中佛罗里达大学的Talat S. Rahman教授和加州大学河滨分校的Ludwig Bartels教授和他们的学生将结合使用扫描隧道显微镜和第一原理电子结构计算，用于成像和理解许多金属表面上金属配位网络的形成。他们将详细探索这些支持的金属配位中心的电子特性，以解决诸如 (i) 电荷转移（分子与基底之间、金属中心与分子以及金属中心与基底之间）以及 (ii) 形状和能量等特性分子轨道及其与传统金属有机化学的关系。通过适当选择基底电子特性来调整金属中心的有效氧化态和配体 HOMO-LUMO 间隙，将为局部化学和几何环境的变化提供描述符。此外，将寻求定义表面上金属中心周围的配位几何形状的一般规则，并将测试具有特定几何形状（例如，三角形与正方形）的配位中心的稳定性条件。 还将关注了解金属配位中心的磁性特征：将追求共同产生稳定磁网络的金属中心/分子/基底组合。该项目将为研究生提供最先进的建模和/或实验室经验本科生和初级科学家将学习化学合成、各种金属表面金属配位网络的形成、成像和互补的从头算电子结构计算技术。该项目包括对金属表面配位化学的系统探索，这将为建立将其与控制溶液相金属有机化学的传统配体场和晶体场理论区分开来的规则提供框架。对系统的振动和磁特性以及色散力的特殊作用的检查将为所提出的工作增加进一步的价值。通过理论家的领导，该项目肯定会产生系统的理解、更深入的见解、更快地验证研究结果及其对其他系统的推广。拟议的工作预计将通过以确定性方式提供对金属协调网络的访问，对工业方法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化，这对于大范围的微电子、光电和磁性应用来说是重要的。这项工作还将为教育和外展活动提供机会，这些活动已被证明具有广泛的国家、国际和社会影响。