Collaborative Research: Directing molecular assemblies into covalently bonded 2D organic materials

合作研究：将分子组装成共价键合的二维有机材料

• 批准号: 1904654
• 负责人: Elena Galoppini
• 金额: $ 32万
• 依托单位: Rutgers University Newark
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2023-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1904654&HistoricalAwards=false
• 关键词: Collaborative; Research; Directing; molecular; assemblies

Professors Robert Bartynski and Sylvie Rangan of Rutgers University New Brunswick and Professor Elena Galoppini of Rutgers University Newark are supported by the Macromolecular, Supramolecular and Nanochemistry (MSN) Program in the Division of Chemistry of the National Science Foundation to develop new methods for the creation of carbon-based two-dimensional materials on metal surfaces. Ordered arrays of custom designed molecular building blocks are assembled on single crystal surfaces then subjected to an external stimulus, such as heat, light, or energetic electrons, to link together neighboring molecules creating an extended two-dimensional sheet material. The topology and functionality of the sheet are controlled by judicious selection and placement of the chemical building blocks prior to exposure to the external stimulus. The resulting sheets hold the promise of displaying a wide variety of novel properties and phenomena such as new forms of magnetism, conduction of electricity with little or no resistance, and efficient emission or absorption of light. Success of this research project opens the way to new applications of two-dimensional materials in nano-electronics, sensors, solar cells, light-emitting diodes, and other devices that require processability, tunability, high performance, and properties that cannot be obtained with conventional materials. During the course of conducting the project, the students involved are broadly trained in a multidisciplinary science research environment and provided a chance to interact with scientists in national laboratories. Undergraduate students from under-represented minority groups are involved in the project and high school students and teachers are mentored. The project generates a "toolbox" for on-surface synthesis of two-dimensional (2D) materials. Different bonding mechanisms that are relevant to on-surface synthesis are explored and ways to create a hierarchy of surface reactions to direct the formation of intermolecular C-C bonds between molecular units to create new 2D organic systems are developed. The toolbox involves (a) the development of specially designed molecular precursors with functional groups placed at strategic positions, (b) the use of inter-molecular and/or intra-molecular interactions between functional groups, as well as surface templating effects on textured metals, to control the assembly of the molecular precursors on single crystal surfaces. A particular emphasis is placed on the formation of C-C bonds by dehydrogenation (elimination of H2), dehalogenation (elimination of X2, X = Br, Cl, I) and dehydrofluorination (elimination of HF) reactions. The nature of the resulting 2D structures are studied through an integrated combination of surface science techniques, including scanning tunneling microscopy, and the electronic properties are examined through a combination of synchrotron-based electron spectroscopies, direct and inverse photoemission as well as ab-initio theoretical methodsThis 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.

罗格斯大学新不伦瑞克省的罗伯特·巴蒂恩斯基（Robert Bartynski）和西尔维·兰根（Sylvie Rangan）和罗特格斯大学（Rutgers University Newark）的Elena Galoppini教授得到了纽瓦克（Newark）的支持。 定制设计的分子构件的有序阵列组装在单晶表面上，然后受到外部刺激（例如热，光或能量电子），以将相邻的分子链接在一起，从而产生延长的二维板材材料。 纸的拓扑和功能是通过在暴露于外部刺激之前的明智选择和化学构建块的位置来控制的。 所得的床单具有显示各种新型特性和现象的希望，例如新形式的磁性形式，几乎没有或没有阻力的电力传导以及有效的发射或光吸收。 该研究项目的成功为二维材料在纳米电子，传感器，太阳能电池，发光二极管以及其他需要可加工性，可调性，高性能和无法用常规材料无法获得的特性的设备方面开辟了道路。 在进行该项目的过程中，参与的学生在多学科科学研究环境中进行了广泛的培训，并提供了与国家实验室中科学家互动的机会。 来自代表不足的少数群体的本科生参与了该项目，高中生和老师得到了指导。 该项目生成一个“工具箱”，用于二维（2D）材料的地下合成。 探索了与地面合成相关的不同键合机制，并创建表面反应的层次结构以指导分子之间分子间C-C键的形成，以创建新的2D有机系统。 该工具箱涉及（a）具有官能团在战略位置的特殊设计的分子前体的发展，（b）使用官能团之间的分子间和/或分子间和/或分子内相互作用，以及对纹理金属的表面模板作用，以控制单晶表面上分子前体的组装。 特殊的重点是通过脱氢（消除H2），去alogenation（消除X2，X = BR，Cl，I）和脱氢氟化（消除HF）反应而特别强调。 通过表面科学技术的集成组合（包括扫描隧道显微镜检查）研究所得2D结构的性质，并通过基于同步体的直接和逆光光学光谱以及AB-INITIO MERTER INTERCTION INFRACTICTARTIONS的构建原理的构建范围来检查，并通过基于同步的电子光谱的组合来检查电子特性，并经过构建的构建范围。和更广泛的影响审查标准。

项目成果

Dehydrofluorination as a Residue-Free Selective Route to C–C Bond Formation at Metal Surfaces

• DOI: 10.1021/acs.jpcc.2c00712
• 发表时间: 2022-03
• 期刊: The Journal of Physical Chemistry C
• 作者: J. Viereck;Yang Zhang;E. Galoppini;R. Bartynski;S. Rangan

Synthesis and study of fluorine-functionalized ZnTPPs

氟功能化ZnTPPs的合成与研究

• DOI: 10.1142/s1088424622500146
• 发表时间: 2022
• 期刊: Journal of Porphyrins and Phthalocyanines
• 影响因子: 1.5
• 作者: Zhang, Yang;Viereck, Jonathan;Rangan, Sylvie;Bartynski, Robert;Galoppini, Elena
• 通讯作者: Galoppini, Elena