Porphene: How Is It Formed?

在化学结构动力学和机制-B（CSDM-B）计划的支持下，科罗拉多大学的Josef Michl教授将研究锌卟啉在水面上氧化聚合成二维聚合物卟啉的机理。 金属卟啉是一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图案化单片电路板。 拟议的机械调查的目的是促进他们从实验室的好奇心转化为实际有用的材料，并教育和培训早期的职业科学家。二维聚合物片是一个非常感兴趣的对象，因为它们在纳米技术的承诺，但其形成的机制是不完全理解。 卟啉正方形网格产生于水氧化剂表面上的单体锌卟啉，通过去除每个单体上外围的12个氢原子并形成12个新的C-C键。 这种氧化聚合产生了非常大的单晶域上的数百纳米的顺序，并显示热力学和动力学控制的功能。 一个原位动力学和机械的调查，这种反应，使用各种工具的建议，如果成功的话，由此产生的洞察力将允许进一步增加域的大小和减少缺陷density.This奖项反映了NSF的法定使命，并已被认为是值得通过使用该基金会的智力价值和更广泛的影响审查标准进行评估的支持。

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.