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ASTM Selected Technical Papers
Advances in Luminescence Spectroscopy
By
LJ Cline Love
LJ Cline Love
1
Seton Hall University
, Chemistry Department
South Orange, NJ 07079
;
symposium co-chairman and co-editor
.
Search for other works by this author on:
D Eastwood
D Eastwood
2
U.S. Army Corps of Engineers Missouri River Division Laboratory
?
420 S. 18th St., Omaha NE 68102
;
symposium co-chairman and co-editor
.
Search for other works by this author on:
ISBN-10:
0-8031-0412-X
ISBN:
978-0-8031-0412-9
No. of Pages:
134
Publisher:
ASTM International
Publication date:
1985

The photo-excitation steps in 3-hydroxyflavone leading to proton-transfer are described. The consequence of the ultra-rapid (<8 ps) phototautomerization is the emission of a unique yellow-green tautomer fluorescence (λmax 525 nm) in hydrocarbon solution, instead of the violet fluorescence expected from the first UV absorption (onset λ 370 nm, first peak λ 354 nm). The tautomerization is intramolecular, involving the transfer of the hydroxyl hydrogen to the neighboring carbonyl group of the 3-hydroxyflavone molecule.

The analytical applications suggested by the qualitative spectroscopic features investigated result from the extreme sensitivity of the intramolecular H-bond to external solvent perturbations, which appear most strikingly in low-temperature spectroscopic studies as induced violet fluorescences of the H-bonded solvates. Using solute concentrations of 10−5 to 10−7M, H-bonding impurities are detectable at substoichiometric concentrations. In the case of water in hydrocarbon solvents, the present experiments suggest that 10−7 to 10−9M water may be detectable.

Ethers, alcohols, water, and other H-bonding solvents give characteristic violet solvate fluorescence band contours and peak positions, permitting qualitative discrimination of trace contaminants. The use of 3-hydroxyflavone as a fluorescence probe for solvent impurities is suggested. An application is made of isolated-site crystal matrix spectroscopy to determine the intrinsic low-temperature spectroscopic behavior of solutes, such as quinones and ketones, which can H-bond with trace impurities.

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