Physik Department E20, Technische Universität München, D-85748 Garching, Germany.
ACS Nano. 2013 May 28;7(5):4520-6. doi: 10.1021/nn401171z. Epub 2013 May 3.
The fabrication and control of coordination compounds or architectures at well-defined interfaces is a thriving research domain with promise for various research areas, including single-site catalysis, molecular magnetism, light-harvesting, and molecular rotors and machines. To date, such systems have been realized either by grafting or depositing prefabricated metal-organic complexes or by protocols combining molecular linkers and single metal atoms at the interface. Here we report a different pathway employing metal-organic chemical vapor deposition, as exemplified by the reaction of meso-tetraphenylporphyrin derivatives on atomistically clean Ag(111) with a metal carbonyl precursor (Ru3(CO)12) under vacuum conditions. Scanning tunneling microscopy and X-ray spectroscopy reveal the formation of a meso-tetraphenylporphyrin cyclodehydrogenation product that readily undergoes metalation after exposure to the Ru-carbonyl precursor vapor and thermal treatment. The self-terminating porphyrin metalation protocol proceeds without additional surface-bound byproducts, yielding a single and thermally robust layer of Ru metalloporphyrins. The introduced fabrication scheme presents a new approach toward the realization of complex metal-organic interfaces incorporating metal centers in unique coordination environments.
在明确的界面处制造和控制配位化合物或体系是一个蓬勃发展的研究领域，有望应用于多个研究领域，包括单分子催化、分子磁性、光捕获以及分子转子和机器。迄今为止，这些体系是通过在界面处接枝或沉积预制的金属有机配合物，或者通过将分子配体和单个金属原子组合在一起来实现的。在这里，我们报告了一种不同的途径，采用金属有机化学气相沉积法，例如在真空条件下，原子级清洁的 Ag(111)表面上的间四苯基卟啉衍生物与金属羰基前体（Ru3(CO)12）反应。扫描隧道显微镜和 X 射线光谱揭示了间四苯基卟啉环脱氢产物的形成，该产物在暴露于 Ru-羰基前体蒸气和热处理后很容易发生金属化。自终止卟啉金属化方案在没有额外的表面结合副产物的情况下进行，生成了一层单一且热稳定的 Ru 金属卟啉。所提出的制造方案为实现包含独特配位环境的金属中心的复杂金属-有机界面提供了一种新方法。
