Graduate Thesis Or Dissertation
 

The solid state photochemistry and photophysics of a triphenylmethyl dye cyanide

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  • Triphenylmethyl dye cyanides have been known to be sensitive to ultraviolet radiation since early in this century. Under appropriate conditions, exposure to uv leads to heteropolar fission of the C-CN bond (photoionization) and intense coloration due to dye formation. Thin homogeneous films of hexahydroxyethyl pararosaniline cyanide in a nylon matrix (Far West Technology) have been used to study the photochemistry of the dye cyanide in a solid medium and also to investigate its potential as a uv dosimeter. The dye cyanide in nylon absorbs strongly in the uv ([superscript ε] max= 6.25 x 10⁴ liter mole-¹ cm-¹ at 277 nm) and dye is produced by excitation at wavelengths < 340 nm. The dye absorbs strongly in the red region ([superscript ε] max = 7.0 x 10⁴ liter mole-¹ cm-¹ at 608 nm). The extent of photoionization may thus be determined from the optical density in the red region. In addition, the dye has been found to fluoresce when excited with a helium-neon laser at 633 nm and this property may also be used to follow the course of photolysis. The film response is reproducible, stable after exposure for many days, and dose-rate independent. However, at room temperature the partitioned quantum yield for dye formation varies from 0.4 at 260 nm to about 1 at 340 nm. Furthermore, the quantum yield is strongly dependent on the temperature during photolysis. These features limit the use of the film as an integrating actinometer for erythemal uv, but it should be valuable as a routine laboratory actinometer for monochromatic radiation. A model is presented to account for the observed photochemical behavior.
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