title: Different formation kinetics and photoisomerization behavior of self-assembled monolayers of thiols and dithiolanes bearing azobenzene moieties.
abstract: Self-assembled monolayers (SAMs) containing azobenzene moieties are very attractive for a wide range of applications, including molecular electronics and photonics, bio-interface engineering and sensoring. However, very little is known about the aggregation and photoswitching behavior that azobenzene units undergo during the SAM formation process. Here, we demonstrate that the formation of thiol-based SAMs containing azobenzenes (denoted as AzoSH) on gold surfaces is characterised by a two-step adsorption kinetics, while a three-step assembly process has been identified for dithiolane-based SAMs containing azobenzenes (denoted AzoSS). The H-aggregation on the AzoSS SAMs was found to be remarkably dependent on the time of self-assembly, with less aggregation as a function of time. While photoisomerization of the AzoSH was suppressed for all different assembly times, the reversible trans-cis photoisomerization of AzoSS SAMs formed over 24 hours was clearly observed upon alternating UV and Vis light irradiation. We contend that detailed information on formation kinetics and related optical properties is of crucial importance for elucidating the photoswitching capabilities of azobenzene-based SAMs.
authors.affiliation: School of Chemical Engineering, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK.
authors.forename: Chun L
authors.initials: CL
authors.lastname: Yeung
authors.forename: Scott
authors.initials: S
authors.lastname: Charlesworth
authors.forename: Parvez
authors.initials: P
authors.lastname: Iqbal
authors.forename: James
authors.initials: J
authors.lastname: Bowen
authors.forename: Jon A
authors.initials: JA
authors.lastname: Preece
authors.forename: Paula M
authors.initials: PM
authors.lastname: Mendes
mesh_terms: D001391:Azo Compounds / Q000737:chemistry*; D007536:Isomerism; D007700:Kinetics; D008027:Light; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D014466:Ultraviolet Rays
chemical_list: D001391:Azo Compounds; D013438:Sulfhydryl Compounds; C009850:azobenzene