title: Modulation of unconventional fluorescence of novel photochromic perimidine spirodimers.
abstract: Fluorescence modulation by a class of photochromic perimidine spirodimers, which exhibit a characteristic fluorescence associated with their photochromic reactions, has been described. Upon irradiation using 365 nm light, these non-fluorescent spiro molecules undergo a thermally-reversible ring opening at their spiro junction resulting in the generation of strong fluorescence. The fluorescing species is distinctly different from both the stable ring-closed and the ring-opened compounds, though it appears to have been formed from and remains in equilibrium with the photochemically generated ring-opened form. While the fluorescing species possesses a narrow absorption band with its maximum centered at 500 nm, the ring-opened form exhibits a broad absorption across the visible region with two maxima centered at 410 and 650 nm, respectively. After initiating the photochromic reactions in these molecules using 365 nm light, purely photochemically-controlled fluorescence modulation can be carried out using two wavelengths in the visible region, that is, 500 and 700 nm, while the equilibrium concentration of the ring-opened form and the fluorescing species is controlled. Fluorescence modulation is attained also by controlling the ratio of the ring-closed and ring-opened forms by photochemical ring-opening and thermal ring-closing reactions. The study on the effect of substitution of these molecules suggests that by extending the conjugation of the perimidine core in the ring-opened form the molecule is rendered non-fluorescent and hence it can be assumed that the perimidine core forms the fluorescing entity of the molecule.
authors.affiliation: Molecular Smart System Group, Nanotechnology Research Institute, National Institute of Advanced Industrial Science and Technology, Central 5, Higashi, 1-1-1, Tsukuba, Ibaraki 305 8565, Japan.
authors.forename: Riju
authors.initials: R
authors.lastname: Davis
authors.forename: Nobuyuki
authors.initials: N
authors.lastname: Tamaoki