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Optical and magnetic properties of the lowest triplet state of pyrido(2,3-b)pyrazine. An example of /sup 3/n. pi. * azanaphthalene

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100291a016· OSTI ID:6802308

The lowest excited triplet (T/sub 1/) states of pyrido(2,3-b)pyrazine(2,3-b)pyrazine (PP; 1,4,5-triazanaphthalene) in the three kinds of environments have been studied by using various spectroscopic and magnetic resonance techniques. The authors obtained phosphorescence emission and excitation spectra, triplet lifetimes, zero field splittings (zfs), and triplet sublevel properties. From the analysis of the results the authors conclude that T/sub 1/ is /sup 3/n..pi..* in character in a single crystal of durene and in ethanol, but it is /sup 3/..pi pi..* in trifluoroethanol. Observation of the /sup 3/n..pi..* phosphoresence was made for the first time in azanaphthalenes, which provides direct information about /sup 3/n..pi..* azanaphthalene. The 0-0 band and vibronic bands involving a' vibrations are dominant in the phosphorescence spectrum. Large zfs and negative D (identical with -3/2X; -3.1 GHz) were obtained. As for the sublevel properties T/sub z/ is the most active and T/sub x/ is inactive in both radiative and nonradiative processes, whereas T/sub y/ is moderately active in the T/sub 1/ approx...-->.. S/sub 0/ nonradiative decay process. These /sup 3/n..pi..* properties were discussed in comparison with those of /sup 3/..pi pi..* PP and azanaphtalenes and numbern..pi..* azabenzenes. Possible mechanisms to explain the radiative and nonradiative properties are given.

Research Organization:
Kyoto Univ., Japan
OSTI ID:
6802308
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:7; ISSN JPCHA
Country of Publication:
United States
Language:
English