Journal of Physical Chemistry B, Vol.118, No.29, 8905-8913, 2014
Dielectric Dependence of Single-Molecule Photoluminescence Intermittency: Nile Red in Poly(vinylidene fluoride)
The dependence of single-molecule photoluminescence intermittency (PI) or "blinking" on the local dielectric constant (epsilon) is examined for nile red (NR) in thin films of poly(vinylidene fluoride) (PVDF). In previous studies, variation of the local dielectric constant was accomplished by studying luminophores in chemically and structurally different hosts. In contrast, the NR/PVDF guest-host pair allows for the investigation of PI as a function of epsilon while keeping the chemical composition of both the luminophore and host unchanged. The solvatochromic properties of NR are used to measure the local epsilon, while fluctuations in NR emission intensity over time provide a measure of the PI. PVDF is an ideal host for this study because it provides submicron-sized dielectric domains that vary from nonpolar (epsilon approximate to 2) to very polar (epsilon approximate to 70). The results presented here demonstrate that the local dielectric environment can have a pronounced effect on PI. We find that the NR emissive events increase 5-fold with an increase in epsilon from 2.2 to 74. A complex dependence on epsilon is also observed for NR nonemissive event durations, initially increasing as epsilon increases from 2.2 to 3.4 but decreasing in duration with further increase in epsilon. The variation in emissive event durations with epsilon is reproduced using a photoinduced electron-transfer model involving electron transfer from NR to PVDF. In addition, an increase in NR photostability with an increase in epsilon is observed, suggesting that the dielectric environment plays an important role in defining the photostability of NR in PVDF.