Clair Sylvain, Pons Stéphane, Fabris Stefano, Baroni Stefano, Brune Harald, Kern Klaus, Barth Johannes V
Institut de Physique des Nanostructures, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland.
J Phys Chem B. 2006 Mar 23;110(11):5627-32. doi: 10.1021/jp057239s.
We report scanning tunneling microscopy observations on the formation of 2D Co-based coordination compounds on the reconstructed Au(111) surface. Preorganized arrays of Co bilayer islands are shown to be local reaction sites, which are consumed in the formation of Co-terephthalate aggregates and regular nanoporous grids. The latter exhibit a planar geometry stabilized by the smooth substrate. The nanogrids are based on a rectangular motif, which is understood as an intrinsic feature of a 2D cobaltous terephthalate sheet and dominates over the templating influence of the quasihexagonal substrate atomic lattice. The dynamics of the Co island dissolution and metallosupramolecular self-assembly could be monitored in situ. Complementary first-principles calculations were performed to analyze the underlying driving forces and to examine general trends in 2D metal-carboxylate formation. The findings indicate the wide applicability of coordination chemistry concepts at surfaces, which moreover can be spatially confined by using templated substrates, and its potential to synthesize arrangements unavailable in bulk materials.
我们报告了关于在重构的Au(111)表面上二维钴基配位化合物形成的扫描隧道显微镜观察结果。已表明预先形成的钴双层岛阵列是局部反应位点，它们在钴对苯二甲酸酯聚集体和规则纳米多孔网格的形成过程中被消耗。后者呈现出由光滑衬底稳定的平面几何形状。纳米网格基于矩形图案，这被理解为二维钴对苯二甲酸酯片材的固有特征，并且比准六边形衬底原子晶格的模板化影响更占主导。可以原位监测钴岛溶解和金属超分子自组装的动力学。进行了补充性的第一性原理计算，以分析潜在的驱动力并研究二维金属羧酸盐形成的一般趋势。研究结果表明配位化学概念在表面具有广泛的适用性，而且通过使用模板化衬底可以在空间上对其进行限制，并且其具有合成块状材料中无法获得的排列的潜力。
