Characterization of the spectroscopic properties of a tetrahydrochrysene system containing a rigidified hydroxynitrostilbene chromophore: an inherently fluorescent ligand designed for the estrogen receptor.
A tetrahydrochrysene system that embodies a hydroxy- and nitro-substituted stilbene chromophore held rigidly near planarity by the tetracyclic nature of the compound was prepared as a fluorescent ligand for the estrogen receptor. It shows strong solvent-dependent fluorescence at long wavelengths. The solvent polarity dependence suggests that the fluorescence arises from an excited state with much n pi * character in cyclohexane; stronger emission comes from an intramolecular charge transfer state that has lower energy in more polar solvents, and finally progressive quenching of the charge transfer state occurs in solvents of higher polarity. The quenching effect is particularly evident in protic solvents. In water, however, the compound shows fluorescence of unusually high energy for an intramolecular charge transfer state, which suggests that photochemistry may be occurring. In solutions of gamma-cyclodextrin, emission from the nitrotetrahydrochrysene is red shifted and intensified relative to water. Photobleaching occurs in H2O but not in ethanol or gamma-cyclodextrin solution. The change in dipole moment between the ground and excited states for the nitrochrysene is 12.9 D, similar to our previous measurements for related nitrostilbenes. The compound displays red-shifted emission in triethylamine, perhaps due to an excited state hydrogen-bonded complex. The absorption and emission properties of the corresponding nitrophenolate were also studied. The nitrophenolate exhibits reverse solvatochromism in its absorption spectra. In conclusion, the high sensitivity of the emission energy and quantum yield of the title compound make it of potential utility as a fluorescent probe.
Anstead
G M
GM
Department of Chemistry, University of Illinois, Urbana 61801.
Hwang
K J
KJ
Katzenellenbogen
J A
JA
D001943:Breast Neoplasms / Q000737:chemistry; D002911:Chrysenes / Q000737:chemistry* / Q000378:metabolism; D005260:Female; D005456:Fluorescent Dyes / Q000737:chemistry* / Q000378:metabolism; D006801:Humans; D015394:Molecular Structure; D009574:Nitro Compounds / Q000737:chemistry* / Q000378:metabolism; D011960:Receptors, Estrogen / Q000032:analysis* / Q000378:metabolism; D012997:Solvents; D013053:Spectrophotometry; D013267:Stilbenes / Q000737:chemistry*
D002911:Chrysenes; D005456:Fluorescent Dyes; D009574:Nitro Compounds; D011960:Receptors, Estrogen; D012997:Solvents; D013267:Stilbenes; C081501:2-nitro-5,11-diethyl-5,6,11,12-tetrahydrochrysen-8-ol