title: Contrasting Solid-State Fluorescence of Diynes with Small and Large Aryl Substituents: Crystal Packing Dependence and Stimuli-Responsive Fluorescence Switching.
abstract: There has been a significant current interest in solid state luminescence of organic molecules and their stimuli responsive fluorescence switching behavior. Although small organic derivatives with olefinic, acetylenic, phenylenevinylenic, phenyleneethynylenic spacers are widely documented as solid state emitters in the literature, the solid state photophysics of organic derivatives with "butadiyne" spacer still remains unexplored. We provide detailed investigation on the solid state fluorescence properties of a series of butadiynyl fluorophores. Replacement of a phenyl ring, which is at periphery of the butadiyne bridge, with a large moiety such as pyrenyl group furnishes contrasting emissions in the solid state. While the butadiyne bridged phenyl derivatives show a blue shift of emission maxima in the solid powder with respect to monomer spectra in solution state, the butadiyne bridged pyrenyl derivatives exhibit a red shift in the solid state. The blue shift of the emission maxima of the butadiyne bridged phenyl derivatives in the solid powder is attributed to allowed excitonic transition in aggregates with nearly parallel transition dipoles. On the other hand, formation of pyrenyl excimer accounts for the red shift of the butadiyne bridged pyrenyl derivatives in the solid powder. In addition to that, the solid state fluorescence of the pyrenyl analogues is reversibly switched between two aggregate forms through external heating and rubbing stimuli.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Madras , Chennai 600036, Tamil Nadu, India.
authors.forename: Avik Kumar
authors.initials: AK
authors.lastname: Pati
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai 400076, India.
authors.forename: Santosh J
authors.initials: SJ
authors.lastname: Gharpure
authors.affiliation: Department of Chemistry, Indian Institute of Technology Madras , Chennai 600036, Tamil Nadu, India.
authors.forename: Ashok K
authors.initials: AK
authors.lastname: Mishra