Synthesis of tetra-oligothiophene-substituted calix[4]arenes and their optical and electrochemical properties |
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| Affiliation: | 1. Institute of Chemical Technology, Prague, Technická 5, 16628 Praha, Dejvice, Czech Republic;2. Donostia International Physics Center (DIPC), P.O. Box 1072, 20018 San Sebastián – Donostia, Spain;3. Instituto de Carboquímica, ICB-CSIC, P.O. Box 549, 50080 Zaragoza, Spain;4. Department of Organic Chemistry I, Universidad del País Vasco – Euskal Herriko Unibertsitatea (UPV/EHU), P° Manuel de Lardizabal 3, 20018 San Sebastián – Donostia, Spain;5. Ikerbasque, Basque Foundation for Science, E-48011 Bilbao, Spain;1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun, Jilin 130024, People’s Republic of China;2. College of Resources and Environmental Science, Jilin Agricultural University, Changchun 130118, People’s Republic of China;1. Institute of Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, SK-845 38 Bratislava, Slovakia;2. Department of Organic Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, Slovakia;1. Department of Organic Chemistry, Faculty of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland;2. Institute of Physical and Theoretical Chemistry, Faculty of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland |
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| Abstract: | ![]()
A facile and efficient approach to synthesize tetra-oligothiophene-substituted calix[4]arenes, Calix-OT(n) with n up to 4 using palladium-catalyzed Kumada coupling of thienylmagnesium bromide and bromo-substituted calix[4]arene as a key step has been developed. The close proximity of the tetra-oligothiophenes constructed within a calix[4]arene assembly leads to peak/band broadening, spectral shifting, i.e., blue-shift in absorption and red-shift in emission spectra as well as fluorescence quantum yield quenching as compared to those of monomers indicating the existence of chromophoric interaction. We have shown that the intra-chromophoric interaction lowers the first ionization (raises HOMO level) of an oligothiophene within an assembly. It also stabilizes the formation of a radical cation, which results in an increase in the subsequent voltammetric oxidation and the occurrence of the higher oxidation states as compared to the monomeric counterparts. This assembly can serve as a model for the investigation of molecular interaction of π-conjugated systems. |
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