Chemoselective Adsorption of Allyl Ethers on Si(001): How the Interaction between Two Functional Groups Controls the...

Selective adsorption of multifunctional molecules is rarely observed when the different functional groups react via nonactivated reaction channels. Although the latter is also the case for ether cleavage and the adsorption of C=C double bonds on the highly reactive Si(001) surface, we find that allyl ethers, which combine both functional groups, react on Si(001) selectively via the cleavage of the molecules' ether group. In addition, our XPS measurements at 90, 150, and 300 K indicate an increased reactivity of the ether group when compared to monofunctional ethers. STM investigations furthermore reveal different final adsorption configurations after ether cleavage of allyl methyl ether when compared to diethyl ether as the monofunctional reference molecule. The interaction of the two functional groups in one molecule thus leads to new reaction channels with higher reactivity for ether cleavage on Si(001). As a further consequence, the reactivity of the C=C double bond is suppressed up to room temperature, leading to the observed selective adsorption.