Oligophenylenevinylenes (OPV) with a series of distance-controlling, electron-donating, and/or electron-withdrawing substituents are deposited from vapor phase and solution as ultrathin films or nanoparticles with diameters of 20−200 nm. In some cases the systems are doped at levels of 10-5−10-3 with energy accepting OPV's of longer chainlengths. Absorption and fluorescence spectra, steady-state and time-resolved anisotropies, and radiative and nonradiative deactivation rates of these systems are investigated and compared to the corresponding properties in dilute solutions. Fluorescence yields of the parent oligomers and their alkyl or oxyalkyl derivatives are high in solution with an “infinite chain” limit of ΦF ≈ 0.5 and an upper radiative rate constant limit of k r ∞ = (1 ± 0.3) × 109 s-1. Yields and k r decrease strongly in films and nanoparticles because of H-aggregate formation. However, doping with fluorescent acceptors can increase the yields up to ΦF → 0.7. Introduction of electron-withdrawing -CN and -SO2CF3 substituents reduces ΦF in low viscous dilute solutions almost to zero. High viscosities and condensation to solid phases will raise the yields up to ΦF → 0.6 because of suppression of nonradiative torsional deactivation and formation of J-aggregates with high k r.

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Described is the synthesis and characterization of three poly(p-phenylenevinylene) (PPV) three-ring model compounds, one unsubstituted at the vinylene moiety (1) and two dicyanosubstituted compounds (2, 3), differing in the positions of their cyano groups. Single-crystal analyses of the two cyano-substituted compounds 2 and 3 show that introduction of cyano groups into alkyl-substituted PPV analogous compounds leads to remarkable torsion of the conjugated backbones unlike hexyloxy-substituted compounds. In the case of introducing it into the R-position as in 2, the torsion is distributed almost equally over the molecule. Introducing the cyano group into the -position as in 3 leads to a one-sided torsion between the inner phenylene ring and the vinylene-CN planes.

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