title: Photochromic bis(thiophen-3-yl)maleimides studied with time-resolved spectroscopy.
abstract: The dynamics of the ring-closure reaction of three different bis(thiophen-3-yl)maleimides are investigated using ultrafast spectroscopy in the visible range. The structures of the molecules differ with respect to substitution of the thiophene ring and the maleimide. The experiments reveal reaction kinetics which point to the population of an excited electronic state for several nanoseconds. In the case of completely unsubstituted thiophene rings, a long excited-state lifetime (biexponential decay with 3 and 15 ns) can be observed. The remaining ultrafast absorption transients of this molecule are due to relaxational processes on the excited electronic potential energy surface. The ring-closure reaction has a small yield (<1%) and does not show up in the ultrafast absorption experiments. A dimethyl substitution of the thiophene ring results in completely different behavior: after transients related to relaxation in the excited electronic state, one finds pronounced absorption transients with tau = 16 ps which represent the partial decay of the excited electronic state and the formation of the ring-closed isomer. Another fraction of the emitting excited electronic state decays again on the few nanosecond time scale. The experiments suggest that the open isomer of the dimethyl-substituted imides exists in two conformations.
authors.affiliation: Munich Center for Integrated Protein Science, CIPSM, and Lehrstuhl für BioMolekulare Optik, Department Physik, Ludwig-Maximilians-Universität München, Oettingenstrasse 67, D-80538 München, Germany.
authors.forename: C
authors.initials: C
authors.lastname: Elsner
authors.forename: T
authors.initials: T
authors.lastname: Cordes
authors.forename: P
authors.initials: P
authors.lastname: Dietrich
authors.forename: M
authors.initials: M
authors.lastname: Zastrow
authors.forename: T T
authors.initials: TT
authors.lastname: Herzog
authors.forename: K
authors.initials: K
authors.lastname: Rück-Braun
authors.forename: W
authors.initials: W
authors.lastname: Zinth
mesh_terms: D003116:Color; D005030:Ethylenes / Q000737:chemistry; D005453:Fluorescence; D008027:Light; D008301:Maleimides / Q000737:chemistry*; D055668:Photochemical Processes; D013056:Spectrophotometry, Ultraviolet; D013997:Time Factors
chemical_list: D005030:Ethylenes; D008301:Maleimides; C036216:ethylene