We have prepared high-quality, densely packed, self-assembled monolayers (SAMs) of carboxy-terminated alkyl chains on Si(111). The samples were made by thermal grafting of methyl undec-10-enoate under an inert atmosphere and subsequent cleavage of the ester functionality to disclose the carboxylic acid end-group. X-ray photoelectron spectroscopy (XPS) and grazing incidence X-ray diffraction (GIXD) indicate a surface coverage of about 50% of the initially H-terminated sites. In agreement, GIXD implies a rectangular unit mesh of 6.65 and 7.68 Å side lengths, containing two molecules in a regular zigzag-like substitution pattern for the ester- and carboxy-terminated monolayer. Hydrolysis of the remaining H-Si(111) bonds at the surface furnished HO-Si(111) groups according to XPS and attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) studies. The amide-terminated alkyl SAM on Si(111) assembled in a 2-(6-chloro-1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HCTU)-mediated one-pot coupling reaction under an inert atmosphere, whereby the active ester forms in situ prior to the reaction with an amino-functionalized photoswitchable fulgimide. ATR-FTIR and XPS studies of the fulgimide samples revealed closely covered amide-terminated SAMs. Reversible photoswitching of the headgroup was read out by applying XPS, ATR-FTIR, and difference absorption spectra in the mid-IR. In XPS, we observed a reversible breathing of the amide/imide C1s and N1s signals of the fulgimide. The results demonstrate the general suitability of HCTU as a reagent for amide couplings to carboxy-terminated alkyl SAMs and the on-chip functionalization toward photoswitchable Si(111) surfaces.

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Creating photoactive monolayers of photochromes is of considerable technological interest. This paper describes the construct of fulgimide monolayers on silicon surfaces and presents a quantitative IR analysis studies of their composition and switching properties. The scheme on top shows the structure of the starting C-form terminated Si(111) surface and the graph below sketches the surface composition at the photostationnary states under visisble and UV irradiation, as derived from in situ IR spectroscopy after several UV/vis irradiation cycles.

We report the preparation, through palladium-catalyzed transformations, of the indolylfulgimide linker conjugate 1, containing an adamantane core and nitrile anchoring groups. The ethynylene-linker 12 for the final Sonogashira coupling was prepared through palladium-mediated cyanation of an iodo-substituted precursor with Zn(CN) 2 . The synthesis of the 6-bromo-substituted indolylfulgimide coupling partner 2 was accomplished in seven steps. Model studies using phenylacetylene and the 5-bromo-substituted indole 13 were con-

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