Evolution of absorption, fluorescence, laser and chemical properties in the series of compounds perylene, benzo(ghi)perylene and coronene

Absorption, fluorescence and laser properties of perylene, benzo(ghi)perylene and coronene are studied experimentally (under the same conditions) and quantum chemically at room (293 K) and at low (77 and 4 K) temperatures and direct comparison is made between the results for each molecule. All the main absorption and fluorescence parameters such as oscillator strength, f e, quantum yield, γ, decay time, τ f, fluorescence rate constant, k f (Einstein coefficient, A) and intersystem crossing rate constant, k ST, are measured or calculated. The systems of singlet and triplet levels for these compounds are simulated and analyzed. Triplet states mixing with the lowest singlet S 1 state are determined. The low values of k ST found are explained. The possible vibronic coupling in the molecule coronene is discussed. The nature of the three fluorescence bands of coronene observed is interpreted. The change in the arrangement of the singlet and triplet levels of the studied compounds is interpreted quantum-chemically. It is found that at room temperature (293 K), only perylene shows laser action, while all three compounds show good laser oscillation at low temperature (