Starting from a Fixed Geometry: Real-Time XPS Investigation of a Surface Reaction with Controlled Molecular Configurations
Starting from a Fixed Geometry: Real-Time XPS Investigation of a Surface Reaction with Controlled Molecular Configurations
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DOI：
10.1021/acs.jpcc.0c07743
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发表时间：
2020-10-15
影响因子：
3.7
通讯作者：
Duerr, Michael
中科院分区：
文献类型：
--
作者：
Glaser, Timo;Laenger, Christian;Duerr, Michael
研究了硅单晶(001)表面的乙醚裂解，以确定乙醚基团相对于硅衬底的精确构型。为了保持反应物之间的固定取向，通过环辛炔的应变三键在Si(001)面上化学选择性地连接了环辛炔醚。在这种构型中，这种双功能分子的醚基保持不变，其相对于底物的几何构型由作为连接物的环辛炔环给出。然后用同步辐射实时X射线光电子能谱研究了醚基在高温下的进一步反应动力学。推导出了一个较低的活化势垒，并根据实验中实现的受控构型与潜在的反应机理进行了解释。
Ether cleavage on the silicon (001) surface was investigated for a well-defined configuration of the ether group with respect to the underlying Si substrate. In order to maintain the reactants in a fixed orientation with respect to each other, cyclooctyne ether was chemoselectively attached on Si(001) via the strained triple bond of cyclooctyne. In this configuration, the ether group of this bifunctional molecule remains intact and its geometry with respect to the substrate is given by the cyclooctyne ring as a linker. The kinetics of the further reaction of the ether group at elevated temperatures was then investigated by means of real-time X-ray photoelectron spectroscopy using synchrotron radiation. A low activation barrier was deduced, which is interpreted in terms of the controlled configurations realized in the experiment in correlation with the underlying reaction mechanism.