Temperature-dependent tail-tail dynamics of pyrene-labeled poly(dimethylsiloxane) oligomers dissolved in ethyl acetate.

We have determined the tail-tail dynamics and energetics of linear poly(dimethylsiloxane) (PDMS) polymers (M(n) = 3100; M(w)/M(n) = 1.07) that have been terminally labeled with pyrene (Py-PDMS-Py) in ethyl acetate between 255 and 323 K. The upper critical solution temperature (theta(u)) for the PDMS/ethyl acetate system is 278 K. The Py-PDMS-Py photophysics follow the Birks model at all of the temperatures studied. However, there is evidence for an increase in the local composition of PDMS surrounding the Py- residues in Py-PDMS-Py below the theta temperature. The recovered activation energy for Py-PDMS-Py tail-tail cyclization is the same as the activation energy for diffusion in ethyl acetate. The activation energy for cyclization is about fourfold larger in comparison to the barrier for PDMS internal backbone rotations. The estimated internal activation barrier for Py-PDMS-Py in ethyl acetate is in line with the internal barrier rotation for PDMS backbone rotation. The intramolecular excimer binding energy for Py-PDMS-Py in ethyl acetate is similar to the intermolecular pyrene excimer. In the ground state, the mean distance between the Py-PDMS-Py tail segments does not change over the temperature range studied. A comparison of these temperature-dependent Py-PDMS-Py/ethyl acetate results with previous results on Py-PDMS-Py in pure supercritical CO2 and CO2-dilated liquids shows that the addition of CO2 to the liquid phase offers the way to tune to Py-PDMS-Py tail-tail dynamics over the greatest range.