The pH-dependent orientation of N3 dye on a gold substrate is revealed using heterodyne-detected vibrational sum frequency generation spectroscopy.

Abstract

We report on systematic changes to the adsorption geometry of the dye N3 {[cis-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato ruthenium(II)]} on a gold substrate as the pH of the deposition environment is altered. The protonation states of the four -COOH groups of the N3 dye change according to the modified pH conditions, thus affecting the number of -COOH and -NCS functional groups that participate in the adsorption to gold. Here, we use heterodyne detected vibrational sum frequency generation (HD-VSFG) spectroscopy to obtain surface specific vibrational information on both -COOH and -NCS groups as a function of pH of the deposition conditions. Polarization-dependent HD-VSFG yields sets of complex χ(2) spectra, enabling us to perform a simultaneous fitting procedure to the polarization-dependent real and imaginary components and thus extract detailed structural information of the N3/gold interface. Our results show that N3 preferentially adsorbs to gold either with two -COOH groups and one -NCS group in more acidic conditions or with one -COOH group and two -NCS groups in more basic conditions.