Abstract
The characterisation of the excited state of a molecule implies the determinations of the different quantum yields and lifetimes. Additionally, complex kinetic systems are frequently observed and need to be solved. In this contribution, we give our particular way of studying systems of organic molecules where we describe how a quantum yield of fluorescence (in fluid or rigid solution, or in film), phosphorescence, singlet oxygen and intersystem crossing can be experimentally determined. This includes a brief description of the equipments routinely used for these determinations. The interpretation of bi- and tri-exponential decays (associated with proton transfer, excimer/exciplex formation in the excited state) with the solution of kinetic schemes (with two and three excited species), and consequently the determination of the rate constants is also presented. Particular examples such as the excited state proton transfer in indigo (2-state system), the acid–base and tautomerisation equilibria in 7-hydroxy-4-methylcoumarin (3-state system), together with the classical examples of intramolecular excimer formation in 1,1’-dipyrenyldecane (2-state system) and 1,1’-dipyrenylpropane (3-state system) are given as illustrative examples.
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Notes
- 1.
As a general rule, the credibility of the results obtained from the analysis of fluorescence decays should be (with few exceptions) assessed, by checking the interconsistency of results obtained under different experimental conditions (temperature, solvent viscosity and/or polarity and concentration, among others, e.g. pressure). Changing temperature provides Arrhenius plots of the rate constants, which should be linear. Otherwise, something is wrong with the experiments, or something interesting/new is happening. Changing solvent viscosity (η) provides log–log plots of diffusion-dependent rate constants versus η, which should also be linear (slope = –1) for diffusion-controlled processes (deviations are also interesting) [56–59]. Solvent polarity strongly affects charge and electron transfer processes in a well-known way. For inter-molecular processes, changing the concentration [Q] provides linear plots of the pseudo-unimolecular rate constant k 1 = k bimol[Q] and an accurate value for the bimolecular rate constant, k bimol.
Finally, coupling results from time-resolved fluorescence with those obtained from steady-state experiments are essential in some cases (complex kinetics or low time resolution), and advisable in most other cases. For example, the rate constants obtained from time-resolved experiments can be used to evaluate Stern–Volmer or Stevens–Ban plots (see below) and compare them to those obtained from steady-state experiments. Agreement tells us that everything is alright, while disagreement means that something else is happening, as for example, undetectable short components in the decays (e.g., static quenching and transient effects, see below).
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Seixas de Melo, J.S., Pina, J., Dias, F.B., Maçanita, A.L. (2013). Experimental Techniques for Excited State Characterisation. In: Evans, R., Douglas, P., Burrow, H. (eds) Applied Photochemistry. Springer, Dordrecht. https://doi.org/10.1007/978-90-481-3830-2_15
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