Evidence for On-Site Carboxylation in the Self-Assembly of 4,4′-Biphenyl Dicarboxylic Acid on Cu(111)
Evidence for On-Site Carboxylation in the Self-Assembly of 4,4′-Biphenyl Dicarboxylic Acid on Cu(111)
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DOI：
10.1021/acs.jpcc.5b10394
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发表时间：
2016-01
影响因子：
3.7
通讯作者：
T. Schmitt;L. Hammer;M. A. Schneider
中科院分区：
文献类型：
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作者：
T. Schmitt;L. Hammer;M. A. Schneider
分子在表面的自组装由分子-底物和分子间相互作用之间的复杂平衡控制。表面化学反应的发生将极大地改变相互作用能的支配层次。这方面的一个重要方面是化学反应是否独立于自组装过程发生，从而反应物种形成有序结构，或者该反应是否是自组装过程的组成部分并在有序结构形成过程中被触发。报道了在超高真空中用低温扫描隧道显微镜研究4，4‘-联苯二甲酸在铜(111)面亚单层覆盖下的有序相。对于该体系，热激活的羧化反应对分子结构的形成影响很大。我们发现，有证据表明，在室温附近，分子的去质子化是由邻近分子的特定构型触发的，从而允许分子去质子化。
Molecular self-assembly at surfaces is controlled by a complex balance between molecule–substrate and intermolecular interactions. The occurrence of chemical reactions at the surface will alter the governing hierarchy of interaction energies substantially. An important aspect in this respect is whether the chemical reaction happens independently from the self-assembly process, such that reacted species form ordered structures, or whether the reaction is an integral part of the self-assembly process and is triggered during the formation of ordered structures. We report on a low-temperature scanning tunneling microscopy study of ordered phases of 4,4′-biphenyl dicarboxylic acid on Cu(111) at submonolayer coverage in ultrahigh vacuum. For this system the thermally activated carboxylation reaction influences the formation of molecular structures significantly. We find evidence that near room temperature the deprotonation of a molecule is triggered by the specific configuration of neighboring molecules allowin...