title: Hexaarylbiimidazoles as visible light thiol-ene photoinitiators.
abstract: OBJECTIVE
  The aim of this study is to determine if hexaarylbiimidazoles (HABIs) are efficient, visible light-active photoinitiators for thiol-ene systems. We hypothesize that, owing to the reactivity of lophyl radicals with thiols and the necessarily high concentration of thiol in thiol-ene formulations, HABIs will effectively initiate thiol-ene polymerization upon visible light irradiation.
  
  
  METHODS
  UV-vis absorption spectra of photoinitiator solutions were obtained using UV-vis spectroscopy, while EPR spectroscopy was used to confirm radical species generation upon HABI photolysis. Functional group conversions during photopolymerization were monitored using FTIR spectroscopy, and thermomechanical properties were determined using dynamic mechanical analysis.
  
  
  RESULTS
  The HABI derivatives investigated exhibit less absorptivity than camphorquinone at 469nm; however, they afford increased sensitivity at this wavelength when compared with bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide. Photolysis of the investigated HABIs affords lophyl radicals. Affixing hydroxyhexyl functional groups to the HABI core significantly improved solubility. Thiol-ene resins formulated with HABI photoinitiators polymerized rapidly upon irradiation with 469nm. The glass transition temperatures of the thiol-ene resin formulated with a bis(hydroxyhexyl)-functionalized HABI and photopolymerized at room and body temperature were 49.5±0.5°C and 52.2±0.1°C, respectively.
  
  
  CONCLUSIONS
  Although thiol-enes show promise as continuous phases for composite dental restorative materials, they show poor reactivity with the conventional camphorquinone/tertiary amine photoinitiation system. Conversely, despite their relatively low visible light absorptivity, HABI photoinitiators afford rapid thiol-ene photopolymerization rates. Moreover, minor structural modifications suggest pathways for improved HABI solubility and visible light absorption.
authors.affiliation: Macromolecular Science and Engineering, University of Michigan, Ann Arbor, MI 48109, United States.
authors.forename: Dowon
authors.initials: D
authors.lastname: Ahn
authors.affiliation: Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109, United States.
authors.forename: Sameer S
authors.initials: SS
authors.lastname: Sathe
authors.affiliation: Department of Cariology, Restorative Sciences and Endodontics, University of Michigan , Ann Arbor, MI 48109, United States.
authors.forename: Brian H
authors.initials: BH
authors.lastname: Clarkson
authors.affiliation: Macromolecular Science and Engineering, University of Michigan, Ann Arbor, MI 48109, United States.|Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109, United States.
authors.forename: Timothy F
authors.initials: TF
authors.lastname: Scott
mesh_terms: D003188:Composite Resins / Q000737:chemistry*; D003764:Dental Materials / Q000737:chemistry*; D003793:Dental Restoration, Permanent; D006801:Humans; D055115:Light-Curing of Dental Adhesives; D008422:Materials Testing; D008689:Methacrylates / Q000737:chemistry; D058567:Photoinitiators, Dental / Q000737:chemistry* / Q000528:radiation effects; D018583:Pliability; D011092:Polyethylene Glycols / Q000737:chemistry; D058105:Polymerization; D012995:Solubility; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D003188:Composite Resins; D003764:Dental Materials; D008689:Methacrylates; D058567:Photoinitiators, Dental; D013438:Sulfhydryl Compounds; D011092:Polyethylene Glycols
keywords: Camphorquinone; HABI; Photoinitiator; Thiol–ene