Photophysics and photochemistry of an asymmetrically substituted diazene: a suitable cage effect probe.

The photophysics and photochemistry of (1-biphenyl-4-yl-1-methyl-ethyl)-tert-butyl diazene were thoroughly studied by laser flash photolysis from the picosecond to the microsecond time domain. The compound has favorable features as a radical photoinitiator and as a probe for cage effect studies in liquids, supercritical fluids, and compressed gases. The biphenyl moiety acts as an antenna efficiently transferring electronic energy to the dissociative (1)n,pi* state centered on the azo moiety.

Cage effect in supercritical fluids and compressed gases in the photolysis of an asymmetrically substituted diazene.

We studied the photolysis of (1-biphenyl-4-yl-1-methyl-ethyl)-tert-butyl diazene in supercritical CO(2) and Xe, as well as in compressed Kr. The compound has good solubility in the mentioned fluids, allowing the photolysis measurements to be performed in CO(2) at 1.4 K above T(c) and at pressures as low as 70 bar.

Photoinduced isomerization kinetics of diiodomethane in supercritical fluid solution: local density effects.

The density dependence of diiodomethane photoinduced isomerization in supercritical (sc) CO2, CHF3, and C2H6 was investigated by transient absorption spectroscopy, covering a fluid density range from 0.7 to 2.5 (in reduced units).