Synthesis and detailed photophysical studies of pyrene-based molecules substituted with extended chains

Applications of conjugated organic compounds in the field of electronics and optoelectronics and of pyrene derivatives as fluorescent probes are well established. The synthesis of the novel pyrene-based 2,11-di-tert-butyl-6,7,15,16-tetrakis(alkoxy/alkythio)quinoxaline[2',3':9,10]phenanthro[4,5-abc]phenazine, TQPP-[t-Bu](2)-[XR](4) (X = O, S; R = C(n)H(2n+1)), is reported along with an in-depth spectroscopic characterization and evaluation of their photophysical properties. Despite their larger core size, the reported TQPP materials showed similar fluorescence behavior to that of pyrene itself, with no significant shift in their fluorescence peak. The fluorescence spectra showed peaks corresponding to the monomer and to the excimer. Even though these TQPP compounds showed poor solubility in various solvents, their solvatochromism could be investigated in different solvents ranging from polar solvents such as methanol to nonpolar solvents such as cyclohexane; Stokes shifts, fluorescence lifetimes, fluorescence quantum yields, as well as radiative and nonradiative rate constants are determined for four of these TQPP materials in various solvents. Quantum yields were found to be low for these TQPP compounds in solvents such as tetrahydrofuran (THF), whereas they were relatively higher in cyclohexane and dioxane. Monomer to excimer intensity ratio versus gross solvent scale (E(T)30) and orientation polarizabilty (Delta f) were correlated. Although TQPP-[t-Bu](2)-[XR](4) displayed similar fluorescent emission and excitation behavior as that of pyrene, a relatively smaller lifetime was observed for these compounds compared to that of pyrene.