Distance-dependent fluorescence quenching of p-bis[2-(5-phenyloxazolyl)]benzene by various quenchers

We report results of frequency-domain and steady-state measurements of the fluorescence quenching of p-bis-[2-(5-phenyloxazolyl)]benzene (POPOP) when quenched by bromoform (CHBr₃), methyl iodide (CH₃I), potassium iodide (KI), 1,2,4-trimethoxybenzene (TMB), or N,N-diethylaniline (DEA). The quenching efficiency of these compounds decreased in the order DEA, TMB, KI, CH₃I, CHBr₃. In the case of DEA and TMB the measurements clearly confirm the applicability of the exponential distance-dependent quenching (DDQ) model, in which the bimolecular quenching rate k(r) depends exponentially on the fluorophore-quencher separation r, k(r) = k_a exp[-(r - a)/r_e], where a is the distance of closest approach. Simultaneous analysis of the frequency-domain and steady-state data significantly improved resolution of the recovered molecular parameters k_a and r_e. The data for DEA and TMB cannot be satisfactorily fit using either the Smoluchowski or Collins-Kimball radiation boundary condition (RBC) model. The quenching behavior of the less efficient quenchers KI, CH₃I, and CHBr₃ can be adequately described with both the DDQ and RBC models, but this may be a simple consequence of less efficient quenching. The efficiency of quenching is discussed on the basis of the mechanisms of interaction between the fluorophore and quencher molecules, which involves electron transfer and/or heavy atom effects.