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On-Surface Synthesis of Functionalized Honeycombene Macrocycles and Related Two-Dimensional Polymer Structures

功能化蜂窝大环化合物及相关二维聚合物结构的表面合成

基本信息

批准号：
290068185
负责人：
Professor Dr. Michael Gottfried
金额：
--
依托单位：
Institut für Chemie (IfC)
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2016
资助国家：
德国
起止时间：
2015-12-31 至 2020-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/290068185?language=en
关键词：
Surface Synthesis Functionalized Honeycombene Macrocycles

项目摘要

On-surface synthesis is a promising approach for the modification and functionalization of interfaces and for generating new functional materials. While this approach has found some attention for the synthesis of one- and two-dimensional polymers during the past five years, the on-surface synthesis of large organic molecules is still its infancy. Likewise, suitable reactions for covalent bond formation on surfaces are scarce. Encouraged by our joint preliminary studies in our next-door laboratories, we will combine the expertise in organic synthesis from the Hilt group with the surface science competence in the Gottfried group. Specifically, we will use transition-metal catalyzed methods for the flexible synthesis of (poly)functionalized oligophenylene precursors in combination with ultrahigh-vacuum (UHV) based methods for the synthesis, analysis and characterization of complex macrocycles and polymeric frameworks on metal or metal oxide surfaces. Product analysis will be performed with scanning tunneling microscopy (STM), photoelectron spectroscopy (XPS/UPS) and other methods for full structural and compositional analysis. The following aims will be pursued: (a) On-surface synthesis of large conjugated macrocycles (honeycombenes), which undergo self-assembly to form long-range ordered structures on single-crystal surfaces of metals and metal oxides. (b) Functionalization at the periphery of the honeycombene building blocks will be used for further covalent/coordination linkage as a novel approach to well-defined 2D polymers. (c) The inward-functionalization of the honeycombenes will enable follow-up molecular recognition in the central cavity or secondary assembly processes, e.g., the size control of catalytically active metal nanoparticles. (d) We will attempt to generate various honeycombenes on a milligram scale utilizing unprecedented on-surface synthesis on metal nanoparticles. (e) We intend to identify novel bond formation reactions towards poly-functionalized honeycombenes and related structures, expanding the presently very limited arsenal of suitable on-surface reactions. In particular, catalysis by absorbed adatoms will be explored to generate novel macrocyclic structures, such as molecular dodecagrams, via metal-catalyzed [2+2]-cycloaddition reactions. (f) Finally, the reaction mechanisms of the surface-mediated reactions will be investigated using a combination of surface spectroscopic and microscopic techniques, to establish a basis for a systematic development and optimization of these reactions.

表面合成是界面修饰和功能化以及生成新型功能材料的一种很有前途的方法。虽然在过去的五年中，这种方法在一维和二维聚合物的合成中得到了一些关注，但在表面上合成大型有机分子仍处于起步阶段。同样，在表面上形成共价键的合适反应也很少。受我们在隔壁实验室进行的联合初步研究的鼓舞，我们将把希尔特小组在有机合成方面的专业知识与戈特弗里德小组的表面科学能力结合起来。具体来说，我们将使用过渡金属催化的方法来灵活合成（聚）功能化的聚苯炔前驱体，并结合基于超高真空（UHV）的方法来合成，分析和表征金属或金属氧化物表面的复杂大环和聚合物框架。产品分析将使用扫描隧道显微镜（STM），光电子能谱（XPS/UPS）和其他方法进行全结构和成分分析。将追求以下目标：(a)在表面上合成大型共轭大环（蜂群），在金属和金属氧化物的单晶表面上进行自组装形成远程有序结构。(b)蜂窝蜂构建块外围的功能化将用于进一步的共价/配位连接，作为一种明确定义的二维聚合物的新方法。(c)蜂窝蜂的内功能化将使后续在中心腔或二次组装过程中的分子识别成为可能，例如，催化活性金属纳米颗粒的尺寸控制。(d)我们将尝试利用前所未有的金属纳米颗粒表面合成技术，以毫克为单位生产各种蜂蜜。(e)我们打算确定针对多功能化蜂巢和相关结构的新键形成反应，扩大目前非常有限的合适的表面反应库。特别是，通过金属催化的[2+2]-环加成反应，将探索吸附吸附原子的催化作用，以产生新的大环结构，如分子十二克。(f)最后，将结合表面光谱学和显微技术研究表面介导反应的反应机制，为系统地发展和优化这些反应奠定基础。