Probing interfacial organization in surface monolayers using tethered pyrene. 2. Spectroscopy and motional freedom of the adsorbates.

We have studied the steady-state and time-resolved emission spectroscopy of the pyrene-containing monolayers reported in the previous article, where in this work we have bound the monolayers to SiO(x). We find that these monolayer structures are sensitive to the identity of the solvent overlayer, with the solvent playing a significant role in the organization of the surface-bound monolayers. We discuss our findings in the context of the known polarity dependence of the pyrene emission spectrum and find that the motional freedom of the chromophores varies with both the monolayer composition and the identity of the solvent overlayer. Our data point to the importance of neighbor-neighbor interactions within the monolayer structures in mediating the motional freedom of the tethered pyrene chromophores.