Semifluorinated thiols in Langmuir monolayers - a study by nonlinear and linear vibrational spectroscopies

Diogo Volpati; Anna Chachaj-Brekiesz; Adriano L Souza; Caio Vaz Rimoli; Paulo B Miranda; Osvaldo N Oliveira Jr; Patrycja Dynarowicz-Łątka

doi:10.1016/j.jcis.2015.08.069

Semifluorinated thiols in Langmuir monolayers - a study by nonlinear and linear vibrational spectroscopies

J Colloid Interface Sci. 2015 Dec 15:460:290-302. doi: 10.1016/j.jcis.2015.08.069. Epub 2015 Aug 29.

Authors

Diogo Volpati¹, Anna Chachaj-Brekiesz², Adriano L Souza³, Caio Vaz Rimoli³, Paulo B Miranda³, Osvaldo N Oliveira Jr³, Patrycja Dynarowicz-Łątka²

Affiliations

¹ São Carlos Institute of Physics, University of São Paulo - USP, PO Box 369, 13566-590 São Carlos, SP, Brazil. Electronic address: diogovolpati@gmail.com.
² Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland.
³ São Carlos Institute of Physics, University of São Paulo - USP, PO Box 369, 13566-590 São Carlos, SP, Brazil.

PMID: 26364075
DOI: 10.1016/j.jcis.2015.08.069

Abstract

A series of semifluorinated thiols of the general formula CmF2m+1CnH2nSH (abbr. FmHnSH) have been synthesized and characterized in Langmuir monolayers with surface pressure-area isotherms, complemented with polarization-modulated reflection absorption spectroscopy (PM-IRRAS) and sum-frequency generation (SFG) techniques. A comparative analysis was performed for compounds having the same length of fluorinated segment (F10) and variable length of the hydrogenated part (H6, H10, H12), and having identical hydrogenated segment (H12) connected to a fluorinated moiety of different lengths (F6, F8, F10). For the sake of comparison, an alkanethiol (H18SH) was also examined, and F10H10COOH and F10H10OH molecules were used for helping the assignment of SFG spectra of CH stretches. SFG was applied to investigate the hydrocarbon chain and the terminal CF3 group, while PM-IRRAS was used to probe CF2 groups. The number of gauche defects in the hydrocarbon chain increased with the increasing length of the molecule, either by elongation of the hydrogenated or perfluorinated part. SFG measurements recorded at three polarization combinations (ppp, ssp, sps) enabled us to estimate the tilt angle of the terminal CF3 group in semifluorinated thiol molecules as ranging from 35° to 45°, which is consistent with nearly vertical fluorinated segments. Upon increasing the surface pressure, the fluorinated segment gets slightly more upright, but the hydrocarbon chain tilt increases while keeping the same average number of gauche defects. The extent of disorder in the hydrogenated segment may be controlled by varying the size of the fluorinated segment, and this could be exploited for designing functionalized surfaces with insertion of other molecules in the defect region.

Keywords: Air/water interface; Alkanethiols; Langmuir monolayers; Nonlinear spectroscopy; Polarization-modulated reflection absorption spectroscopy; Semifluorinated alkanes; Sum-frequency generation spectroscopy; Vibrational spectroscopy.