Steps to demarcate the effects of chromophore aggregation and planarization in poly(phenyleneethynylene)s. 2. The photophysics of 1,4-diethynyl-2-fluorobenzene in solution and in crystals

Crystals of 1,4-bis(2-hydroxy-2-methyl-3-butynyl)-2-fluorobenzene 4 have a rich packing structure with four distinct molecules in the unit cell. 4 com plex hydrogen bonding network results in the formation of cofacial trimers, cofacial dimers, and monomers within the same unit cell, Given a remarkabl e opportunity to investigate the effect of aggregation on the photophysics of 1,4-diethynylbenzenes,we analyzed the absorption, diffuse reflectance, a nd emission spectra of compound 4 in solutions and in crystals. Diffuse ref lectance and fluorescence excitation revealed a red-shifted absorption that is absent in dilute solution but becomes observable at high concentrations and low temperatures. The fluorescence emission in the solid state is dual with components assigned to monomers and aggregates, The excitation and em ission assigned to the monomer are nearly identical in crystals and dilute solutions. The absorption and emission bands assigned to aggregates are bro ad and red-shifted by 60-80 nm, As expected for a sample with absorbers and emitters with different energies and incomplete equilibration, efficient m onomer-to-aggregate. energy transfer was observed by a proper selection of excitation wavelengths. The fluorescence quantum yield of 4 in solution is relatively low (Phi (F) = 0.15) and the singlet lifetime short (tau (F) = 3 .8 ns, A lower limit for the triplet yield of Phi (T) = 0.64: was determine d indirectly in solution by O-1(2) sensitization, and a relatively strong a nd long-lived phosphorescence was observed in low-temperature glasses and i n crystals at 77 K.