The geometry relaxation and photodeactivation from the S2 state of dibenzofuran studied by ultrafast spectroscopy

Abstract Dibenzofuran (DBF) has attracted much attention from scientists recently since it is applied as a photoluminescence material and pharmaceutically active compound. Since the polychlorinated derivatives are highly toxic and manifest photostability in the environment. Femtosecond transient absorption spectroscopy associated with quantum chemical calculations are employed to investigate the ultrafast excited state dynamics of dibenzofuran from the S2 state in 1,4-dioxane and ethanol, respectively. Following excitation at a wavelength of 266 nm, the S2 state is firstly populated in the Franck–Condon region and preserves the planar molecular structure of the ground state. The observed increase of the transient absorption spectra of the excited state within the first several picoseconds indicates a geometry relaxation occurring on the S2 potential energy surface. The subsequent kinetic traces of excited state absorption show that the S2 state in the adiabatic region decays to the S1 state through a fast internal conversion, followed by intersystem crossing to the T1 state with a decay time of tens and hundreds of picoseconds in ethanol and 1,4-dioxane, respectively. Finally, the deactivation processes from the S1 or T state are slow and take place on a time scale of about 20 ns.

[1]  C. Näther,et al.  Ultrafast dynamics of the ESIPT photoswitch N-(3-pyridinyl)-2-pyridinecarboxamide. , 2018, Physical chemistry chemical physics : PCCP.

[2]  Bing Zhang,et al.  Ultrafast investigation of photoinduced charge transfer in aminoanthraquinone pharmaceutical product , 2017, Scientific Reports.

[3]  Shunya Takahashi,et al.  Structural elucidation and synthesis of vialinin C, a new inhibitor of TNF-α production. , 2014, Bioorganic & medicinal chemistry.

[4]  T. Itoh,et al.  Fluorescence and nonradiative processes of dioxin vapors. , 2014, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[5]  Jiuyan Li,et al.  Simple bipolar host materials incorporating CN group for highly efficient blue electrophosphorescence with slow efficiency roll-off , 2013 .

[6]  F. Temps,et al.  Ultrafast electronic deactivation dynamics of the rare natural nucleobase hypoxanthine , 2012 .

[7]  Yongjun Lu,et al.  Azaphilones and p-terphenyls from the mangrove endophytic fungus Penicillium chermesinum (ZH4-E2) isolated from the South China Sea. , 2011, Journal of natural products.

[8]  Chu-Hung Lin,et al.  Anti-inflammatory Biphenyls and Dibenzofurans from Rhaphiolepis indica. , 2010, Journal of natural products.

[9]  T. Imasaka,et al.  The S1 ← S0 0–0 transition energies of polychlorinated dibenzofurans (PCDFs) revisited: CIS(D) and MP2 calculations with correction for correlation energies , 2009 .

[10]  V. G. Klimenko,et al.  Effect of the orbital structure and symmetry of electronic states on nonradiative S-T intersystem crossing: Dibenzofuran , 2009 .

[11]  A. Carroll,et al.  Vanillic acid derivatives from the green algae Cladophora socialis as potent protein tyrosine phosphatase 1B inhibitors. , 2007, Journal of natural products.

[12]  I. Ljubić,et al.  Theoretical study of structure, vibrational frequencies, and electronic spectra of dibenzofuran and its polychlorinated derivatives. , 2007, The journal of physical chemistry. A.

[13]  T. Yamanaka,et al.  Vibronic structure in the S1-S0 transition of jet-cooled dibenzofuran. , 2006, The journal of physical chemistry. A.

[14]  Yoshio Tatamitani,et al.  Sub-Doppler high-resolution excitation spectroscopy of the S1 ← S0 transition of dibenzofuran , 2006 .

[15]  J. Yi,et al.  Rotationally resolved S1<-- S0 electronic spectra of fluorene, carbazole, and dibenzofuran: evidence for Herzberg-Teller coupling with the S2 state. , 2006, The Journal of chemical physics.

[16]  A. Machado,et al.  Psoralen analogues: synthesis, inhibitory activity of growth of human tumor cell lines and computational studies. , 2006, European journal of medicinal chemistry.

[17]  M. Ziółek,et al.  Artifacts in femtosecond transient absorption spectroscopy , 2002 .

[18]  N. Nijegorodov,et al.  The influence of molecular symmetry and topological factors on the internal heavy atom effect in aromatic and heteroaromatic compounds. , 2001, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[19]  C. D. De Rosa,et al.  Effects of polychlorinated biphenyls on the nervous system , 2000, Toxicology and industrial health.

[20]  D. Hoyer,et al.  Potent and selective non-peptidic inhibitors of endothelin-converting enzyme-1 with sustained duration of action. , 2000, Journal of medicinal chemistry.

[21]  D. Paustenbach,et al.  Relative susceptibility of animals and humans to the cancer hazard posed by 2,3,7,8-tetrachlorodibenzo-p-dioxin using internal measures of dose , 1998 .

[22]  Christopher L. Brown,et al.  Molecular and Supramolecular Synthesis with Dibenzofuran‐Containing Systems , 1997 .

[23]  W. Lorenz,et al.  Dioxins and furans in the Jordanian environment. Part 2: Levels of PCDD and PCDF in human milk samples from Jordan. , 1996, Chemosphere.

[24]  S. Schlemmer,et al.  Infrared emission spectra of candidate interstellar aromatic molecules , 1996, Nature.

[25]  J. Harborne,et al.  Dibenzofuran phytoalexins from the sapwood tissue of Photinia, Pyracantha and Crataegus species , 1995 .

[26]  D. J. Funk,et al.  Gas-Phase Absorption and Laser-Induced Fluorescence Measurements of Representative Polychlorinated Dibenzo-p-dioxins, Polychlorinated Dibenzofurans, and a Polycyclic Aromatic Hydrocarbon , 1995 .

[27]  J. Kelly,et al.  HYDROPHOBIC CLUSTER FORMATION IS NECESSARY FOR DIBENZOFURAN-BASED AMINO ACIDS TO FUNCTION AS BETA -SHEET NUCLEATORS , 1994 .

[28]  Fischer,et al.  Singlet-exciton transport and spatial and energetic disorder in dibenzofuran crystals. , 1990, Physical review. B, Condensed matter.

[29]  M. Zander,et al.  On the Phosphorescence of Benzologues of Furan , Thiophene , Selenophene , and Tellurophene . A Systematic Study of the Intra -annular Internal Heavy-atom Effect , 1989 .

[30]  Anita C Jones,et al.  Fluorescence excitation spectra and decay times of jet-cooled dibenzofuran and the dibenzofuran-water complex , 1984 .

[31]  A. Bree,et al.  Vibronic coupling in the lowest singlet state of dibenzofuran , 1974 .

[32]  R. Shimada,et al.  Phosphorescence spectra of polycyclic compounds—I: Fluorene and dibenzofuran , 1961 .