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Time-Resolved Transient Optical Absorption Study of Bis(terpyridyl)oligothiophenes and Their Metallo-Supramolecular Polymers with Zn(II) Ion Couplers

By David Rais (1581937), Miroslav Menšík (1581928), Pavla Štenclová-Bláhová (1581931), Jan Svoboda (1581934), Jiří Vohlídal (1442161) and Jiří Pfleger (1442170)


α,ω-Bis­(terpyridyl)­oligothiophenes spontaneously assemble with Zn­(II) ions giving conjugated constitutional dynamic polymers (dynamers) of the metallo-supramolecular class, which potentially might be utilized in optoelectronics. Their photophysical properties, which are of great importance in this field of application, are strongly influenced by the dynamic morphology. It was assessed in this study by using ultrafast pump–probe optical absorption spectroscopy. We identified and characterized relaxation processes running in photoexcited molecules of these oligomers and dynamers and show impacts of disturbed coplanarity of adjacent rings (twisting the thiophene–thiophene and thiophene–terpyridyl bonds by attached hexyl side groups) and Zn­(II) ion couplers on these processes. Major effects are seen in the time constants of rotational relaxation, intersystem crossing, and de-excitation lifetimes. The photoexcited states formed on different repeating units within the same dynamer chain do not interact with each other even at very high excitation density. The method is presented that allows determining the equilibrium fraction of unbound oligothiophene species in a dynamer solution, from which otherwise hardly accessible values of the average degree of polymerization of constitutionally dynamic chains in solution can be estimated

Topics: Biophysics, Biochemistry, Cell Biology, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, Physical Sciences not elsewhere classified, show impacts, relaxation processes, absorption spectroscopy, Zn, photophysical properties, oligothiophene species, Major effects, dynamer solution, photoexcited states, time constants, dynamer chain, photoexcited molecules, hexyl side groups, equilibrium fraction, excitation density
Year: 2015
DOI identifier: 10.1021/jp512213s.s001
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Provided by: FigShare
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