A new series of pure and highly soluble oligodiacetylenes (ODAs) was synthesized in high yield and on a multi-milligram scale by a sequence of Sonogashira reactions with a strongly reduced level of homocoupling. The lambda max and epsilon max of these ODAs show an increase with both chain elongation and solvent polarity. A plot of lambda max absorption versus 1/CL (CL=conjugation length) was shown to be linear. The lambda max converges to 435 nm for the longest members of the series at micromolar concentration. This reveals that the longest wavelength absorption observed for PDA chains (lambda max up to 700 nm) is due to aggregation effects. The fluorescence quantum yield increased from monomer to trimer and decreased for longer ODAs. A similar trend is found for the lifetime of fluorescence with a maximum of 600 ps for the trimer. The observed linearity of the rotational correlation time with the oligomer length implies that the ODA chains in solution lack significant geometrical changes. This implies that the ODAs in solution are fully stretched molecular rods of up to 4 nm in length.

The photophysical properties of a series of monomeric, dimeric and trimeric oligodiacetylenes (ODAs; oligoenynes) bearing trimethylsilyl, t-butyl and n-octyl end-capping substituents were studied in solution and in a polymer film. Emission studies show a significant emission of oligodiacetylenes in solution, which increased with increased conjugation. This is remarkable given the near absence of fluorescence in oligoenes of similar length (e.g. hexatriene) and polydiacetylenes (PDAs), which constitute the conjugation limit. A large Stokes shift was observed, and shown to originate from an energy difference between the Franck-Condon excited state and the fluorescent state. From near-identical angles obtained for the absorption and emission dipoles it was concluded that the overall geometry of ODAs does not significantly change upon electronic transition.

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The excited-state dynamics of an oligomer of polydiacetylene, 2,2,17,17-tetramethyloctadeca-5,9,13-trien-3,7,11,15-tetrayne, dissolved in n-hexane have been studied by femtosecond fluorescence upconversion and polarized transient absorption experiments under one- and two-photon excitation conditions. Spectroscopically monitoring the population relaxation in the excited states in real time results in a distinct time separation of the dynamics. It has been concluded that the observed dynamics can be fully accounted for on the basis of the two lower excited states of the target molecule. The S1 (2(1)Ag) state, which cannot be excited from the ground state with one-photon absorption, is verified to be populated via internal conversion in 200+/-40 fs from the strong dipole-allowed S2 (1(1)Bu) state. The population in the "hot" S1 state subsequently cools with a time constant of 6+/-1 ps and decays back to the ground state with a lifetime of 790+/-12 ps.