We report that the thermal stability of self-assembled monolayers (SAMs) of two isocyanide derivatives (1pentyl isocyanide and benzyl isocyanide) on a gold surface was drastically improved by their preparation at high temperature (373 K). In the case of conventionally prepared isocyanide SAMs, thermal desorption spectroscopy revealed that the isocyanides changed their adsorption states with corresponding increase in binding energy. The results of surface-enhanced Raman scattering spectroscopy measurements also clearly indicated the change in adsorption states at 373 K during heating. Theoretical calculations using density functional theory revealed that there are two stable adsorption states (atop and adatom configurations) and that the calculated vibrational energies are in good agreement with those observed in Raman spectra.
The formation and surface structure of 3-hexylthiophene (HTP) self-assembled monolayers (SAMs) on Au(111) prepared by solution and ambient-pressure vapor deposition at room temperature (RT) for 24 h were examined by means of scanning tunneling microscopy (STM) and cyclic voltammetry (CV). STM imaging revealed that HTP SAMs formed by solution deposition have a disordered phase, whereas those formed by vapor deposition exhibit a striped phase with a unidirectional orientation. The distance between the rows in the striped phase was measured to be 1.3 ± 0.1 nm, and the hexyl molecular backbones of HTP in the SAMs on Au(111) are oriented parallel to the Au(111) surface with the head-to-head orientation. From this STM observation, we suggest that the formation of this striped phase in HTP SAMs prepared by vapor deposition were mainly driven by the optimization of van der Waals interactions between the hexyl chains on the surface. CV measurements also demonstrated that HTP SAMs show a high blocking efficiency for electron transfer reactions between electrolytes and the gold electrode, suggesting the formation of SAMs on Au(111) from the vapor phase. Our results obtained here will be very useful for understanding the formation and structure of HTP SAMs on Au(111) surfaces and how they are influenced by deposition method.
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