title: Computational study on the anomalous fluorescence behavior of isoflavones.
abstract: Isoflavones are known to show fluorescence with intensities that depend strongly on the solvent properties and exhibit Stokes' shifts as large as 1.4 eV. While some of this behavior can be explained by (excited state) deprotonation, this mechanism does not apply for all isoflavones. The aim of this study is to computationally and experimentally investigate the reasons for this anomalous behavior of neutral isoflavones, taking the daidzein molecule as a model compound. We find that the absence in fluorescence in aprotic solvents and the weak fluorescence in protic solvents can be explained by a change of order of the lowest singlet states in which a fluorescent charge-transfer state lies below the nonfluorescent locally excited state in water but not in acetonitrile. The large Stokes' shift is partly due to a significant rotation among the chromone-phenyl bond in the excited state.
authors.affiliation: Amsterdam Center for Multiscale Modeling (ACMM), VU University Amsterdam, Amsterdam, The Netherlands.
authors.forename: S Maya
authors.initials: SM
authors.lastname: Beyhan
authors.forename: Andreas W
authors.initials: AW
authors.lastname: Götz
authors.forename: Freek
authors.initials: F
authors.lastname: Ariese
authors.forename: Lucas
authors.initials: L
authors.lastname: Visscher
authors.forename: Cees
authors.initials: C
authors.lastname: Gooijer
mesh_terms: D000042:Absorption; D003198:Computer Simulation; D005453:Fluorescence; D007529:Isoflavones / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013050:Spectrometry, Fluorescence; D014867:Water / Q000737:chemistry
chemical_list: D007529:Isoflavones; D012997:Solvents; D014867:Water; C004742:daidzein