NCCR Nanoscale Science and Department of Physics, University of Basel, Klingelbergstr. 82, 4056 Basel, Switzerland.
Chemistry. 2010 Feb 15;16(7):2079-91. doi: 10.1002/chem.200902596.
The structural chemistry and reactivity of 1,3,8,10-tetraazaperopyrene (TAPP) on Cu(111) under ultra-high-vacuum (UHV) conditions has been studied by a combination of experimental techniques (scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy, XPS) and DFT calculations. Depending on the deposition conditions, TAPP forms three main assemblies, which result from initial submonolayer coverages based on different intermolecular interactions: a close-packed assembly similar to a projection of the bulk structure of TAPP, in which the molecules interact mainly through van der Waals (vDW) forces and weak hydrogen bonds; a porous copper surface coordination network; and covalently linked molecular chains. The Cu substrate is of crucial importance in determining the structures of the aggregates and available reaction channels on the surface, both in the formation of the porous network for which it provides the Cu atoms for surface metal coordination and in the covalent coupling of the TAPP molecules at elevated temperature. Apart from their role in the kinetics of surface transformations, the available metal adatoms may also profoundly influence the thermodynamics of transformations by coordination to the reaction product, as shown in this work for the case of the Cu-decorated covalent poly(TAPP-Cu) chains.
在超高真空（UHV）条件下，通过实验技术（扫描隧道显微镜（STM）和 X 射线光电子能谱，XPS）和 DFT 计算的组合，研究了 1,3,8,10-四氮杂苝（TAPP）在 Cu（111）上的结构化学和反应性。根据沉积条件的不同，TAPP 形成三种主要的组装体，它们是基于不同分子间相互作用的初始亚单层覆盖的结果：一种类似于 TAPP 体相结构的密堆积组装体，其中分子主要通过范德华（vdW）力和弱氢键相互作用；一种多孔铜表面配位网络；和共价键合的分子链。Cu 衬底对于确定表面上的聚集体和可用反应通道的结构至关重要，这在多孔网络的形成中表现得尤为明显，Cu 衬底提供了用于表面金属配位的 Cu 原子，而在高温下 TAPP 分子的共价偶联中也起到了关键作用。除了在表面转化动力学中的作用外，可用的金属 adatoms 也可能通过与反应产物的配位来深刻影响转化的热力学，如本工作中对于 Cu 修饰的共价聚（TAPP-Cu）链的情况所示。
