title: Bridged photochromic diarylethenes investigated by ultrafast absorption spectroscopy: evidence for two distinct photocyclization pathways.
abstract: Two photochromic diarylethenes blocked by alkyl bridges in an ideal conformation for photocyclization are studied by stationary and femtosecond transient spectroscopy in order to depict the photocyclization processes: the bistable 1,2-dicyano[2.n]metacyclophan-1-ene with n = 2, abbreviated as [2.2], and its non-bistable analogue with n = 4, abbreviated as [2.4]. The data are interpreted in the light of AM1-CIS calculations and state correlation diagrams based on conclusive TD-DFT calculations. For [2.2], a solvent-sensitive excitation wavelength threshold governing the photocyclization yield is clearly evidenced between the S(1) and S(2) singlet states. Excitation above and beyond this threshold induces two distinct photochemical pathways. The S(1) vertical excitation induces direct efficient (phi approximately = 0.9-1), and ultrafast (approximately 120 fs) photocylization from S(1) open form that leads to a ground-state transition structure, probably through a conical intersection, then to a hot cyclized ground state that relaxes by vibrational cooling. Upon higher excitation energy, the system undergoes internal conversion to the hot S(1) state, then evolves toward the cyclized S(1) state and relaxes by ultrafast S(1)-S(0) internal conversion. Alternatively, the possibility for a second conical intersection near hot S(1) state is discussed. This second photoclosure reaction is less efficient and both the photocylization yield and overall kinetics depend on solvent polarity (phi = 0.49, tau = 2.5 ps in nonpolar solvent; phi = 0.7, tau = 1.5 ps in polar solvent). In the case of [2.4], for which the distance between the two reactive carbons is larger, a unique photoclosure mechanism is found and a structural effect is reported. Indeed, this mechanim is similar to the above second reaction of [2.2] but characterized by much slower kinetics ranging from 12 to 20 ps (depending on the excitation wavelength and solvent polarity). All polarity effects are rationalized in terms of stabilization of the transient states of charge-transfer character involved in the photocyclization process.
authors.affiliation: Laboratoire de Spectrochimie Infrarouge et Raman (UMR 8516 du CNRS), Centre d'études et de recherches Lasers et Applications (FR 2416 du CNRS), Université des Sciences et Technologies de Lille, Bat C5, 59655 Villeneuve d'Ascq Cedex, France. stephane.aloise@univ-lille1.fr
authors.forename: Stéphane
authors.initials: S
authors.lastname: Aloïse
authors.forename: Michel
authors.initials: M
authors.lastname: Sliwa
authors.forename: Zuzanna
authors.initials: Z
authors.lastname: Pawlowska
authors.forename: Julien
authors.initials: J
authors.lastname: Réhault
authors.forename: Julien
authors.initials: J
authors.lastname: Dubois
authors.forename: Olivier
authors.initials: O
authors.lastname: Poizat
authors.forename: Guy
authors.initials: G
authors.lastname: Buntinx
authors.forename: Aurélie
authors.initials: A
authors.lastname: Perrier
authors.forename: François
authors.initials: F
authors.lastname: Maurel
authors.forename: Shouhei
authors.initials: S
authors.lastname: Yamaguchi
authors.forename: Michinori
authors.initials: M
authors.lastname: Takeshita