Cross metathesis on olefin-terminated monolayers on Si(111) using the Grubbs' catalyst
Cross metathesis on olefin-terminated monolayers on Si(111) using the Grubbs' catalyst
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DOI：
10.1021/la0532196
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发表时间：
2006-02-28
期刊：
影响因子：
3.9
通讯作者：
Bowden, NB
中科院分区：
文献类型：
--
作者：
Dutta, S;Perring, M;Bowden, NB
本文报道了通过交叉复分解反应在Si（111）表面制备烯烃单分子膜的功能化和图案化。以市售原料为原料，一步合成了双烯烃-CH_2 =CH（CH_2）（9）O（（CH_（29）CH）-C-）= CH_2-。在氢封端的Si（111）表面制备了这种新型双烯烃和1-十八烯的混合单分子膜。烯烃被提升到单层的其余部分之上，因此在空间上可用于进一步官能化。烯烃封端的单层与Grubbs的第一代催化剂和用氟、羧酸、醇、醛和烷基溴封端的烯烃在溶液中反应。使用X射线光电子能谱和水平衰减全反射红外光谱表征这些单分子膜表明，表面上的烯烃通过交叉复分解反应，暴露氟，羧酸，醛，醇和溴化物。通过校准实验，我们证明了组装中使用的溶液中烯烃的比例与混合单层的最终组成之间的简单1：1对应关系。最后，这些硅上的单层图案化的微米尺寸尺度上的软光刻使用微流体通道图案化到聚（二甲基硅氧烷）（PDMS）邮票。微米宽的线的聚合物刷上合成这些单分子膜，其特征在于通过扫描电子显微镜。此外，烯烃封端的单分子层图案化成微米级的线暴露羧酸通过交叉复分解与烯烃在溶液中。这种图案化的方法是广泛适用的，并且可以在包括生物传感器和纳米电子学的开发在内的各种领域中找到应用。
This paper reports the functionalization and patterning of olefin-terminated monolayers on Si(111) through cross metathesis. A simple, one-step synthesis of a diolefin-CH2=CH(CH2)(9)O((CH29CH)-C-)=CH2-was developed from commercially available starting materials. Mixed partially olefin-terminated monolayers of this novel diolefin and 1-octadecene on hydrogen-terminated Si(111) were obtained. The olefins are raised above the rest of the monolayer and thus sterically accessible for further functionalization. Olefin-terminated monolayers were reacted with the Grubbs' first generation catalyst and olefins in solution that were terminated with fluorines, carboxylic acids, alcohols, aldehydes, and alkyl bromides. Characterization of these monolayers using X-ray photoelectron spectroscopy and horizontal attenuated total reflection infrared spectroscopy demonstrated that olefins on the surface had reacted via cross metathesis to expose fluorines, carboxylic acids, aldehydes, alcohols, and bromides. Through calibration experiments, we demonstrated a simple 1:1 correspondence between the ratio of olefins in solution used in the assembly and the final composition of the mixed monolayers. Finally, these monolayers on silicon were patterned on the micrometer-size scale by soft lithography using microfluidic channels patterned into poly (dimethylsiloxane) (PDMS) stamps. Micrometer-wide lines of polymer brushes were synthesized on these monolayers and characterized by scanning electron microscopy. In addition, olefin-terminated monolayers were patterned into micrometer-sized lines exposing carboxylic acids by cross metathesis with olefins in solution. This method of patterning is broadly applicable and can find applications in a variety of fields including the development of biosensors and nanoelectronics.