title: Anion-exchange reactions on a robust phosphonium photopolymer for the controlled deposition of ionic gold nanoclusters.
abstract: UV curing (photopolymerization) is ubiquitous in many facets of industry ranging from the application of paints, pigments, and barrier coatings all the way to fiber optic cable production. To date no reports have focused on polymerizable phosphonium salts under UV irradiation, and despite this dearth of examples, they potentially offer numerous substantial advantages to traditional UV formulation components. We have generated a highly novel coating based on UV-curable trialkylacryloylphosphonium salts that allow for the fast (seconds) and straightforward preparation of ion-exchange surfaces amenable to a roll-to-roll process. We have quantified the surface charges and exploited their accessibility by employing these surfaces in an anion exchange experiment by which [Au25L18](-) (L = SCH2CH2Ph) nanocrystals can be assembled into the solid state. This unprecedented application of such surfaces offers a paradigm shift in the emerging chemistry of Au25 research where the nanocrystals remain single and intact and where the integrity of the cluster and its solution photophysical properties are resilient in the solid state. The specific loading of [Au25L18](-) on the substrates has been determined and the completely reversible loading and unloading of intact nanocrystals to and from the surface has been established. In the solid state, the assembly has an incredible mechanical resiliency, where the surface remains undamaged even when subjected to repeated Scotch tests.
authors.affiliation: Department of Chemistry and Centre for Advanced Materials and Biomaterials Research, The University of Western Ontario, London, Ontario, Canada N6A 5B7.
authors.forename: Ryan
authors.initials: R
authors.lastname: Guterman
authors.forename: Mahdi
authors.initials: M
authors.lastname: Hesari
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Ragogna
authors.forename: Mark S
authors.initials: MS
authors.lastname: Workentin
mesh_terms: D000838:Anions / Q000737:chemistry; D006046:Gold / Q000737:chemistry*; D053768:Metal Nanoparticles / Q000737:chemistry*; D063065:Organophosphonates / Q000138:chemical synthesis / Q000737:chemistry*; D055668:Photochemical Processes; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry*; D014466:Ultraviolet Rays
chemical_list: D000838:Anions; D063065:Organophosphonates; D011108:Polymers; D006046:Gold