Methyl Viologens of Bis‐(4’‐Pyridylethynyl)Arenes – Structures, Photophysical and Electrochemical Studies, and their Potential Application in Biology

Please always quote using this URN: urn:nbn:de:bvb:20-opus-287126
  • A series of bis‐(4’‐pyridylethynyl)arenes (arene=benzene, tetrafluorobenzene, and anthracene) were synthesized and their bis‐N‐methylpyridinium compounds were investigated as a class of π‐extended methyl viologens. Their structures were determined by single crystal X‐ray diffraction, and their photophysical and electrochemical properties (cyclic voltammetry), as well as their interactions with DNA/RNA were investigated. The dications showed bathochromic shifts in emission compared to the neutral compounds. The neutral compounds showed veryA series of bis‐(4’‐pyridylethynyl)arenes (arene=benzene, tetrafluorobenzene, and anthracene) were synthesized and their bis‐N‐methylpyridinium compounds were investigated as a class of π‐extended methyl viologens. Their structures were determined by single crystal X‐ray diffraction, and their photophysical and electrochemical properties (cyclic voltammetry), as well as their interactions with DNA/RNA were investigated. The dications showed bathochromic shifts in emission compared to the neutral compounds. The neutral compounds showed very small Stokes shifts, which are a little larger for the dications. All of the compounds showed very short fluorescence lifetimes (<4 ns). The neutral compound with an anthracene core has a quantum yield of almost unity. With stronger acceptors, the analogous bis‐N‐methylpyridinium compound showed a larger two‐photon absorption cross‐section than its neutral precursor. All of the dicationic compounds interact with DNA/RNA; while the compounds with benzene and tetrafluorobenzene cores bind in the grooves, the one with an anthracene core intercalates as a consequence of its large, condensed aromatic linker moiety, and it aggregates within the polynucleotide when in excess over DNA/RNA. Moreover, all cationic compounds showed highly specific CD spectra upon binding to ds‐DNA/RNA, attributed to the rare case of forcing the planar, achiral molecule into a chiral rotamer, and negligible toxicity toward human cell lines at ≤10 μM concentrations. The anthracene‐analogue exhibited intracellular accumulation within lysosomes, preventing its interaction with cellular DNA/RNA. However, cytotoxicity was evident at 1 μM concentration upon exposure to light, due to singlet oxygen generation within cells. These multi‐faceted features, in combination with its two‐photon absorption properties, suggest it to be a promising lead compound for development of novel light‐activated theranostic agents.show moreshow less

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Author: Goutam Kumar Kole, Marta Košćak, Anissa Amar, Dragomira Majhen, Ksenija Božinović, Zlatko Brkljaca, Matthias Ferger, Evripidis Michail, Sabine Lorenzen, Alexandra Friedrich, Ivo Krummenacher, Michael Moos, Holger BraunschweigORCiD, Abdou Boucekkine, Christoph Lambert, Jean‐François Halet, Ivo Piantanida, Klaus Müller‐Buschbaum, Todd B. Marder
URN:urn:nbn:de:bvb:20-opus-287126
Document Type:Journal article
Faculties:Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie
Fakultät für Chemie und Pharmazie / Institut für Organische Chemie
Language:English
Parent Title (English):Chemistry – A European Journal
Year of Completion:2022
Volume:28
Issue:40
Article Number:e202200753
Source:Chemistry – A European Journal 2022, 28(40):e202200753. DOI: 10.1002/chem.202200753
DOI:https://doi.org/10.1002/chem.202200753
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Tag:DNA/RNA binding; cell imaging; methyl viologen; singlet oxygen; two-photon absorption
Release Date:2023/06/19
Licence (German):License LogoCC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International