Fluorescence and Phosphorescence Spectroscopy. by Stephen G. Schulman

By Stephen G. Schulman

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Extra info for Fluorescence and Phosphorescence Spectroscopy. Physicochemical Principles and Practice

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A solvent which has atoms having lone or nonbonding electron pairs is said to be a hydrogen bond acceptor solvent. Qualitatively, a hydrogen bond donor behaves as a very weak Bronsted acid, partially donating a proton to a basic site on the solute molecule. A hydrogen bond acceptor behaves as a very weak Bronsted base, partially accepting a proton from the solute molecule. Because of the involvement of nonbonding and lone pairs in n ·* π* and intramolecular charge transfer transitions, hydrogen bonding solvents have the greatest effect on the positions of these types of spectra.

G. g. the carbonyl group), enhance charge-transfer by introducing a partial positive charge into the charge-transfer acceptor group. This interaction stabilizes the charge-transfer excited state relative to the ground state so that the absorption spectra shift to longer wavelengths with increasing hydrogen bond donor capacity of the solvent. g. -0Hf -NH 2 ). g. -OH, -NH2)· This is effected by the partial withdrawal of the positively charged proton from the functional group. g. -C-OH), inhibits charge-transfer by leaving a residual negative charge on the functional group.

The B, band of benzenoid and naphthalenoid compounds is allowed by the angular momentum selection rule and is therefore affected only slightly, by changes in solvent. The absorption bands of aromatic hydrocarbons and their derivatives substituted with nonconjugated functional groups are similarly only slightly affected by solvent properties. The intensities of fluorescence and phosphorescence spectra are extremely sensitive to solvent polarity and hydrogen bonding properties. These sensitivities to solvents are in part the result of changes in transition intensity produced by distortion of the π-electron distributions of the luminescing molecules and are thus analogous to the effects of solvent perturbations of the electronic absorption spectra.

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