Chemoselective Reactivity of Bifunctional Cyclooctynes on Si(001)
Chemoselective Reactivity of Bifunctional Cyclooctynes on Si(001)
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DOI：
10.1021/acs.jpcc.6b07501
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发表时间：
2016-11-24
影响因子：
3.7
通讯作者：
Duerr, Michael
中科院分区：
文献类型：
--
作者：
Reutzel, Marcel;Muenster, Niels;Duerr, Michael
硅表面可控有机功能化作为半导体技术的一个组成部分，为其广泛的应用提供了新的前景。然而，硅悬键的高活性阻碍了这种官能化的第一个基本反应步骤，即双功能有机分子在原始的硅表面上的化学选择性连接。我们通过使用环辛烷作为我们战略的主要组成部分来克服这个问题。官能化的环辛炔通过应变的环辛炔三键选择性地在Si(001)面上反应，而侧基保持不变。所获得的选择性来自于不同官能团之间截然不同的吸附动力学：与绝大多数其他有机官能团不同，环辛炔是一种直接吸附途径。后者通过介稳中间体与Si(001)反应，使其与环辛炔的应变三键的直接途径竞争时有效地无反应。
Controlled organic functionalization of silicon surfaces as an integral part of semiconductor technology offers new perspectives for a wide range of applications. The high reactivity of the silicon dangling bonds, however, presents a major hindrance for the first basic reaction step of such a functionalization, that is, the chemoselective attachment of bifunctional organic molecules on the pristine silicon surface. We overcome this problem by employing cyclooctyne as the major building block of our strategy. Functionalized cyclooctynes are shown to react on Si(001) selectively via the strained cyclooctyne triple bond while leaving the side groups intact. The achieved selectivity originates from the distinctly different adsorption dynamics of the separate functionalities: A direct adsorption pathway is demonstrated for cyclooctyne as opposed to the vast majority of other organic functional groups. The latter ones react on Si(001) via a metastable intermediate, which makes them effectively unreactive in competition with the direct pathway of cyclooctyne's strained triple bond.