title: Controlling two-step multimode switching of dihydroazulene photoswitches.
abstract: We present the synthesis and switching studies of systems with two photochromic dihydroazulene (DHA) units connected by a phenylene bridge at either para or meta positions, which correspond to a linear or cross-conjugated pathway between the photochromes. According to UV/Vis absorption and NMR spectroscopic measurements, the meta-phenylene-bridged DHA-DHA exhibited sequential light-induced ring openings of the two DHA units to their corresponding vinylheptafulvenes (VHFs). Initially, the VHF-DHA species was generated, and, ultimately, after continued irradiation, the VHF-VHF species. Studies in different solvents and quantum chemical calculations indicate that the excitation of DHA-VHF is no longer a local DHA excitation but a charge-transfer transition that involves the neighboring VHF unit. For the linearly conjugated para-phenylene-bridged dimer, electronic communication between the two units is so efficient that the photoactivity is reduced for both the DHA-DHA and DHA-VHF species, and DHA-DHA, DHA-VHF, and VHF-VHF were all present during irradiation. In all, by changing the bridging unit, we can control the degree of stepwise photoswitching.
authors.affiliation: Department of Chemistry and Center for Exploitation of Solar Energy, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen (Denmark).
authors.forename: Anne U
authors.initials: AU
authors.lastname: Petersen
authors.forename: Søren L
authors.initials: SL
authors.lastname: Broman
authors.forename: Stine T
authors.initials: ST
authors.lastname: Olsen
authors.forename: Anne S
authors.initials: AS
authors.lastname: Hansen
authors.forename: Lin
authors.initials: L
authors.lastname: Du
authors.forename: Anders
authors.initials: A
authors.lastname: Kadziola
authors.forename: Thorsten
authors.initials: T
authors.lastname: Hansen
authors.forename: Henrik G
authors.initials: HG
authors.lastname: Kjaergaard
authors.forename: Kurt V
authors.initials: KV
authors.lastname: Mikkelsen
authors.forename: Mogens Brøndsted
authors.initials: MB
authors.lastname: Nielsen
keywords: charge transfer; chromophores; conjugation; electrocyclic reactions; photochromism