Low-Energy Ion−Surface Reactions of Pyrazine with Two Classes of Self-Assembled Monolayers: Influence of Alkyl Chain Orientation

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Abstract
Collisions of pyrazine with two classes of self-assembled monolayer (SAM) films are employed to determine whether surface confinement and the resulting alkyl chain orientation, influences low-energy ion−surface reactions. SAM films formed from n-alkanethiols (CH3(CH2)n−S−Au, n = 14−17) and 4-(4-alkoxyphenylbenzenethiols (4-(4-CH3(CH2)mOC6H4)−C6H4−S−Au, m = 14−17) chemisorbed onto Au (111) substrates are known to exhibit a chain-length-dependent odd−even effect that places the terminal C−C bond into different orientations. Ion−surface collisions (20 eV) of pyrazine molecular ion (M = m/z 80) with these surfaces yield reaction product ions corresponding to the addition of hydrogen atoms ([M + H]+ = m/z 81) and methyl groups ([M + CH3]+ = m/z 95) from the surface to the probe ion. Differences in the relative abundance of the reaction product ions are measured as a function of chain length for both classes of SAM film. SAM films with odd chain lengths (n, m = 14 and 16) have a consistently higher abundance of H addition product ions than SAM films with even chain lengths (n, m = 15 and 17). Alternating reactivity is also observed for the addition of CH3, with methyl addition occurring more readily on even-chain-length films. The variations are consistent with the well-characterized orientation differences known to exist for films of this type. Specifically, odd-chain-length films are oriented such that the last C−C bond is more parallel to the plane of the surface than it is for even-chain-length films. The critical element of the parallel orientation is that it leaves, on average, one hydrogen atom on the terminal methyl and both hydrogen atoms on the first underlying methylene in more reactive positions compared to even chain lengths. Conversely, the trend in the relative abundance of CH3 addition indicates that the orientation produced by an even-chain-length film, with the last C−C bond more perpendicular to the surface, allows the probe ion better access to the methyl carbon. Reflection absorption IR spectroscopy (RAIRS) data independently confirm the orientational disposition of the films. The RAIRS data show that the odd−even effect is less dramatic for the n-alkanethiols when compared to 4-(4-alkoxyphenyl)benzenethiols. A smaller difference in ion−surface reactivity is measured for n-alkanethiols, demonstrating that ion−surface reactions can distinguish subtle differences in average orientation. In short, we report that the extent of ion−surface reactions of pyrazine ion with two classes of SAM films is directed by the spatial orientation of the surface-confined species that participate in the reaction.

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