Perturbed sites and host—guest—host exciton cascade in the biphenyl isotopic mixed crystal phosphorescence

An interesting energy cascade is observed in the phosphorescence spectra of 1% biphenyl-h₁₀ in biphenyl-d₁₀ (2–15 K); strongly perturbed host sites, with energy levels below that of the protonated guest, quench the guest sites at higher temperatures (11–15 K). The identification of the perturbed sites is based on vibrational characteristics (both intensity and frequency), obtained with the help of phosphorescence spectra of biphenyl-h₁₀ and biphenyl-d₁₀ in an argon matrix, indicating an isotope dependent vibronic structure. A partial vibrational analysis is presented, resulting in confirmation of the first triplet state of biphenyl as orbitally ungerade. The dynamics of the triplet excitation are discussed, including several possible mechanisms explaining the non-Boltzmann nature of the low-temperature steady state.