Pronounced Odd−Even Changes in the Molecular Arrangement and Packing Density of Biphenyl-Based Thiol SAMs: A Combined STM and LEED Study

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Abstract

Self-assembled monolayers (SAMs) of ω-(4‘-methylbiphenyl-4-yl) alkanethiols CH3(C6H4)2(CH2)nSH (BPn, n = 3 and 4) on Au(111) substrates were studied using scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED). Preparation at elevated temperature results in highly ordered layers with large domains. Whereas the (2√3 × √3) structure of the BP3 SAMs is similar to that reported previously for other aromatic thiols, SAMs made from BP4 exhibit a very different structure. A (5√3 × 3)rect unit cell containing 8 molecules is found which corresponds to a packing density reduced by 25% compared to that of BP3. The odd−even effect observed in the molecularly resolved STM images of BP3 and BP4, therefore, confirms the pronounced influence of the spacer chain on the structure of these biphenyl-based SAMs.

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