Oligo(para‐phenylene) (OPP) derivatives bearing photoresponsive chiral dithienylethene (DE*) terminal moieties that induce chirality in the OPP main chain are synthesized. In the assembled state, the photoisomerization of the chiral DE* terminal moieties prior to assembly, from the open to the closed form, leads to a change in the helicity of the π‐stacked structures. The circular dichroism spectra of mixed solvent solutions and cast films of the OPP assemblies exhibit bisignate Cotton effects in the absorption region associated with the oligomer main chain: these features indicate the presence of helically π‐stacked structures. Furthermore, the chiral transcription of racemic poly(bithiophenethiophene) (PBTT) by chiral OPP in the assembled state is demonstrated. The chirally transcribed PBTT shows a change in helicity upon the photoisomerization of the chiral DE* terminal moieties of OPP. To the best of our knowledge, this is the first report of helicity control of a helically π‐stacked conjugated oligomer through the photoisomerization of a chiral photoresponsive moiety. Such assemblies could be attractive for use in optoelectronic devices and optical memory systems.
Visual observations through a microscope and in situ Raman measurements have been made for single crystalline ethylene hydrate (EH) and binary methane-ethylene hydrate (MEH) at pressures up to 3.7 GPa and room temperature. Both hydrates showed pressure-induced phase transitions at 1.6, 2.0, and 3.0 GPa for EH and at 1.7, 2.1, and 3.3 GPa for MEH. The cubic sI phase of EH and MEH remains stable up to 1.6 and 1.7 GPa, respectively, which are more widely ranging values than the values for the methane hydrate sI phase. In this sI phase of binary MEH, the cage occupancies by methane and ethylene molecules are investigated from Raman spectra. Above P = 3.0 GPa for EH and 3.3 GPa for MEH, they decomposed by associating with the formation of the polyethylene.
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