Porphene: How Is It Formed?

在化学结构动力学和机理- b （CSDM-B）项目的支持下，科罗拉多大学博尔德分校的Josef Michl教授将研究锌卟啉在水面氧化聚合到二维聚合物卟烯的机理。金属卟啉是一大类新型可调纳米材料，在纳米技术中有着广泛的应用前景，如用于柔性分子电子学的可模式化单片电路板。提出的机械调查旨在促进它们从实验室的好奇心到实际有用的材料的转变，并教育和培训早期职业科学家。二维聚合物薄片由于其在纳米技术方面的前景而成为当前人们极大兴趣的对象，但其形成机制尚不完全清楚。卟烯方形栅格是由水溶液氧化剂表面的锌卟啉单体通过去除每个单体外围的12个氢原子和形成12个新的C-C键而产生的。这种氧化聚合产生了数百纳米大小的单晶结构域，并显示出热力学和动力学控制的特点。提出了使用各种工具对该反应进行原位动力学和机理研究，如果成功，所得到的见解将允许进一步增加畴尺寸和减少缺陷密度。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Structure Dynamics and Mechanisms-B (CSDM-B) Program, Professor Josef Michl at the University of Colorado, Boulder will investigate the mechanism of oxidative polymerization of Zn porphyrin to the two-dimensional polymer porphene on a water surface. Metalloporphenes are a large family of new tunable nanomaterials which promise a variety of applications in nanotechnology, such as patternable monolithic circuit boards for flexible molecular electronics. The proposed mechanistic investigation is intended to promote their transformation from a laboratory curiosity to practically useful materials and to educate and train early career scientists. Two-dimensional polymer sheets are an object of great current interest because of their promise in nanotechnology, but the mechanism of their formation is incompletely understood. The porphene square grid arises from monomeric Zn porphyrin on the surface of an aqueous oxidant through the removal of 12 hydrogen atoms on the periphery on each monomer and the formation of 12 new C-C bonds. This oxidative polymerization produces remarkably large single crystalline domains on the order of hundreds of nanometers and shows features of both thermodynamic and kinetic control. An in situ kinetic and mechanistic investigation of this reaction using a variety of tools is proposed and, if successful, the resulting insight will permit further increase in domain size and decrease in defect density.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.