Previously unreported intense absorption band and the pK/sub A/ of protonated triplet methylene blue
Excitation by a Q-switched giant ruby laser (1.2 joule output at 694 nm, approx. 50 nsec flash) of 2-10 ..mu..M solutions of methylene blue in water, 30% ethanol in water or 50 v/v% water - CH/sub 3/CN at pH values in the range 2.0 - 9.3 converted the dye essentially completely to its T/sub 1/ state. The absorption spectrum of T/sub 1/ dye was measured in different media at pH 2.0 and 8.2 by kinetic spectrophotometry. Previously reported T-T absorption in the violet in acidic and alkaline solutions and in the near infrared in alkaline solution was confirmed. Values found for these absorptions in the present work with 30% ethanol in water as solvent are lambda/sub max/ approx. 370 nm, epsilon/sub max/ approx. 13,200 M/sup -1/ cm/sup -1/ at pH 2 and lambda/sub max/ approx. 420 nm, epsilon/sub max/ approx. 9,000 M/sup -1/ cm/sup -1/, lambda/sub max/ approx. 840 nm, epsilon/sub max/ approx. 20,000 M/sup -1/ cm/sup -1/ at pH 8.2. Long-wavelength T-T absorption in acidic solution is reported here for the first time: lambda/sub max/ approx. 680 nm, epsilon/sub max/ approx. 19,000 M/sup -1/ cm/sup -1/ in 30% ethanol in water at pH 2. Observation of a pH-independent isobestic point approx. 720 nm confirms that the long-wavelength absorptions are due to different protonated states of the same species, MB/sup +/(T/sub 1/) and MBH/sup 2 +/(T/sub 1/). The pK/sub A/ of MBH/sup 2 +/(T/sub 1/) in water was determined from the dependence on pH of absorption at 700 and 825 nm to be 7.1/sub 4/ +- .1 and from the kinetics of decay of triplet absorption to be 7.2. The specific rate of protonation of MB/sup +/(T/sub 1/) by H/sub 2/PO/sub 4//sup -/ in water at pH 4.4 was found to be 4.5 +- .4 x 10/sup 8/ M/sup -1/ sec/sup -1/.
- Research Organization:
- Boston Univ., MA (USA). Dept. of Chemistry
- DOE Contract Number:
- EY-76-S-02-2889
- OSTI ID:
- 5641985
- Report Number(s):
- COO-2889-6
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
METHYLENE BLUE
EXCITED STATES
DYES
RUBY LASERS
TRIPLETS
AMINES
AZINES
CHLORIDES
CHLORINE COMPOUNDS
DRUGS
ENERGY LEVELS
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
LASERS
MULTIPLETS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHENOTHIAZINES
SOLID STATE LASERS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)