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The effect of low‐energy (50 eV) electron irradiation on self‐assembled monolayers (SAMs) of aromatic selenolates on polycrystalline Au{111} was studied by synchrotron‐based X‐ray photoelectron spectroscopy and near‐edge X‐ray absorption fine structure spectroscopy. As a test system, SAMs of biphenylselenolate (BPSe) were used, and analogous biphenylthiolate (BPT) SAMs were taken as a reference. The BPSe films were found to exhibit the expected high stability of aromatic SAMs toward electron irradiation, primarily mediated by the dominance of cross‐linking between the individual molecular species. The cross‐sections of the most prominent irradiation‐induced processes in the BPSe SAMs were obtained and found to be in a range of 0.07–0.2 × 10–16 cm2. Comparison of the BPSe and BPT SAMs showed a higher stability of the former system toward electron irradiation. This phenomenon was explained by a combined effect of a higher degree of crystallinity of the BPSe SAMs and a higher strength of the selenolate‐gold as compared to thiolate‐gold bond. The latter aspect is an important result of the present study, which may help to rationalize the current controversy regarding the relative strength of these two anchor groups. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
