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Triazole-tethered ferrocene-quinoline conjugates: solid-state structure analysis, electrochemistry and theoretical calculations

Ferrocenyl-, triazole- and quinoline-containing compounds are known to possess potential for biological activities. The synthesis 15 and biological activities of O-alkylated quinoline derivatives, attached to the ferrocene moiety through 1, 2, 3-triazole bridge, have 16 been reported earlier. Compounds in which triazole ring is directly bonded to ferrocene skeleton were more active in terms of 17 cytotoxicity and reactive oxygen species generation, as compared to those analogues which contain a spacer between triazole ring 18 and ferrocene skeleton. The first aimof this paper was to explore how small difference on surface of the molecules influence their 19 supramolecular assembling. For these reasons, we performed detailed X-ray crystal structure analysis of five ferrocene-quinoline 20 conjugates. In addition, as electronic structure and electrochemical properties could be important for antiproliferative activities of 21 these conjugates, electrochemical measurements and computational analysis have been performed. In all structures, C-H···N and 22 C-H···F hydrogen bonds form one-dimensional or two-dimensional networks, which are further linked by C-H···π and π···π 23 interactions into higher order supramolecular structures. Conformational search at theM06L level revealed that crystal structures 24 of ferrocene conjugates retained their geometries in solution. This confirmed that solid-state structural properties are relevant for 25 electrochemistry and bioactivity discussion. Derivatives in which triazole ring is directly coupled to the ferrocene have lower 26 redox potential values, which suggest higher antioxidant capacity. This was supported by DFT calculation in which frontier 27 molecular orbitals were used as descriptors for redox behaviour of the respective ferrocene conjugates.

ferrocene ; triazole ; quinoline ; X-ray diffraction ; electrochemistry ; DFT calculations

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