Nanofold‐decorated surfaces from the electrodeposition of di‐alkyl‐cyclopentadithiophenes. (19th December 2017)

• Record Type: Journal Article
• Authors: Szczepanski, Caroline R.; Darmanin, Thierry; Godeau, Guilhem; Guittard, Frédéric
• Is Part Of: Polymers for advanced technologies. Volume 29:Number 3(2018)
• Page Start: 1170
• Page End: 1181
• Publication Date: 2017-12-19
• Subjects: electrodeposition -- electropolymerization -- nanostructures -- superhydrophobicity -- surfaces; Polymers -- Periodicals; 668.9
• DOI: 10.1002/pat.4228
• Languages: English
• ISSNs: 1042-7147

Abstract

Abstract : This work describes the synthesis and subsequent electrodeposition of 4H‐ cyclopenta[2, 1‐ b :3, 4‐ b ′]dithiophene (cyclopentadithiophene) monomers di‐substituted with alkyl chains. Each monomer was electropolymerized in solution to observe their capacity at creating well‐structured, rough surfaces. The length of the alkyl chain substituent has a significant influence on the overall surface morphology and wetting behavior after electropolymerization. In the case of nonsubstituted cyclopentadithiophene monomers or those with short alkyl (methyl and ethyl) substituents, the polymerization proceeds readily, forming rough surfaces that follow the Wenzel regime of wetting. In these cases, the surfaces were decorated with globular agglomerates and woven mat features. The measured surface roughness decreases with alkyl chain length as steric hindrance caused by the alkyl substituents limits electropolymerization. As the alkyl chain substituent increases to propyl chain length and beyond, the increase in steric hindrance is so significant that the surface morphology formed during electrodeposition is primarily due to π‐stacking interactions between very short oligomers formed in solution. With propyl and butyl substituents, nanofold morphology is observed, leading to surfaces with much higher contact angles with water (~132°) that follow the Cassie‐Baxter regime of wetting. This type of surface morphology has only been demonstrated one other time and with the use of fluorinated constituents. This work exposes a mild, fluorine‐free synthetic route to creating nanofold‐decorated surfaces.