title: Opening a spiropyran ring by way of an exciplex intermediate.
abstract: A molecular dyad has been synthesized in which the main chromophore is a 1,4-diethynylated benzene residue terminated with pyrene moieties, this latter unit acting as a single chromophore. A spiropyran group has been condensed to the central phenylene ring so as to position a weak electron donor close to the pyrene unit. Illumination of the pyrene-based chromophore leads to formation of a fluorescent exciplex in polar solvents but pyrene-like fluorescence is observed in nonpolar solvents. The exciplex has a lifetime of a few nanoseconds and undergoes intersystem crossing to the pyrene-like triplet state with low efficiency. Attaching a 4-nitrobenzene group to the open end of the spiropyran unit creates a new route for decay of the exciplex whereby the triplet state of the spiropyran is formed. Nonradiative decay of this latter species results in ring opening to form the corresponding merocyanine species. Rate constants for the various steps have been obtained from time-resolved fluorescence spectroscopy carried out over a modest temperature range. Under visible light illumination, the merocyanine form reverts to the original spiropyran geometry so that the cycle is closed. Energy transfer from the pyrene chromophore to the merocyanine unit leads to an increased rate of ring closure and serves to push the steady-state composition in favor of the spiropyran form.
authors.affiliation: Molecular Photonics Laboratory, School of Natural Sciences, Bedson Building, Newcastle University, Newcastle Upon Tyne, NE1 7RU, United Kingdom. a.c.benniston@ncl.ac.uk
authors.forename: Andrew C
authors.initials: AC
authors.lastname: Benniston
authors.forename: Anthony
authors.initials: A
authors.lastname: Harriman
authors.forename: Sarah L
authors.initials: SL
authors.lastname: Howell
authors.forename: Peiyi
authors.initials: P
authors.lastname: Li
authors.forename: Donocadh P
authors.initials: DP
authors.lastname: Lydon