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

Author(s)

Volpati, Diogo ^[1] ; Chachaj-Brekiesz, Anna ^[2] ; Souza, Adriano L. ^[1] ; Rimoli, Caio Vaz ^[1] ; Miranda, Paulo B. ^[1] ; Oliveira, Jr., Osvaldo N. ^[1] ; Dynarowicz-Latka, Patrycja ^[2]

Affiliation

^[1] Univ Sao Paulo, Sao Carlos Inst Phys, BR-13566590 Sao Carlos, SP - Brazil

^[2] Jagiellonian Univ, Fac Chem, PL-30060 Krakow - Poland

• Document type: Journal article
• Source: Journal of Colloid and Interface Science; v. 460, p. 290-302, DEC 15 2015.
• Web of Science Citations: 3

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 (F-10) and variable length of the hydrogenated part (H-6, H-10, H-12), and having identical hydrogenated segment (H-12) connected to a fluorinated moiety of different lengths (F-6, F-8, 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 perflu-orinated 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. (C) 2015 Elsevier Inc. All rights reserved. (AU)

• FAPESP's process: 12/09905-3 - Spectroscopic evaluation of the bulk and interfacial molecular orientations of organic thin films deposited onto different surfaces
• Grantee: Diogo Volpati
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 13/06595-6 - Applying Langmuir-Blodgett and self-assembled monolayers of semifluorinated alkane derivatives to tune the metal work functions in OLED devices
• Grantee: Osvaldo Novais de Oliveira Junior
• Support Opportunities: Research Grants - Visiting Researcher Grant - International
• FAPESP's process: 14/01595-0 - Investigating interfaces in polymeric optoelectronic devices by SFG spectroscopy
• Grantee: Roberto Mendonça Faria
• Support Opportunities: Regular Research Grants
• FAPESP's process: 13/08864-4 - Molecular control in nanostructured films of carbon nanotubes
• Grantee: Diogo Volpati
• Support Opportunities: Scholarships abroad - Research Internship - Post-doctor