The oxidative cyclization of (E,E)‐2′‐hydroxycinnamylideneacetophenones 1a–e, and (E, E)‐2′‐benzyloxy‐6′‐hydroxycinnamylideneacetophenones 1i–l with DMSO/iodine, gave (E)‐2‐styrylchromones 3a–e,i–l. However, in the case of (E, E)‐γ‐alkyl‐2′‐hydroxycinnamylideneacetophenones 1f–h, (E)‐ and (Z)‐2‐styrylchromones 3f–h and 4f–h were obtained. The stereochemistry of the (E,E)‐cinnamylideneacetophenones 1 and (E)‐ and (Z)‐2‐styrylchromones 3 and 4 was established by NOE experiments. The induced daylight photooxidative cyclization of some (E)‐2‐styrylchromones 3a,f–h gave 12H‐benzo[a]xanthene‐12‐ones 6a,f–h.

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The self-association equilibrium constants, Kass, for the dimerization of some small oligothiophenes in acetone, acetonitrile and chloroform were measured by (1)H NMR spectroscopy. The gas phase interaction energies for some oligothiophene dimers were determined by computational quantum chemistry. The (1)H NMR results indicate that Kass generally increases with the chain length (the number of thienyl rings, n) and solvent polarity; however, Kass for thiophene (n = 1) was found to be higher than for the bithiophenes (n = 2). The linear oligothiophenes 2,2'-bithiophene and 2,2',5',2''-terthiophene were found to self-associate less than their corresponding nonlinear isomers 3,3'-bithiophene and 3,2',5',3''-terthiophene in solution and in the gas phase. For α-quaterthiophene (n = 4) Kass in solution was found to be smaller than expected. The non-linear dependence of the standard molar Gibbs energy of self-association, ΔassG, on the chain length in solution could be nicely reproduced and related to the conformational entropy change of dimerization. It was observed that the melting properties of oligothiophenes correlate well with their tendency to self-associate, with more self-association leading to increased liquid stability, and thus lower melting temperatures. These results highlight the relevance of self-association in isotropic systems for the correct molecular interpretation of phase equilibria.

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