4-OH coumarin based rotary switches: Tautomeric state and effect of the stator. (January 2021)

• Record Type: Journal Article
• Authors: Yordanov, Dancho; Deneva, Vera; Georgiev, Anton; Vassilev, Nikolay; Vala, Martin; Zhivkov, Ivaylo; Antonov, Liudmil
• Is Part Of: Dyes and pigments. Volume 184(2021)
• Publication Date: 2021-01
• Subjects: 4-Hydroxycoumarin -- Rotary switch -- Molecular spectroscopy -- DFT -- Tautomerism -- Photochemistry; Dyes and dyeing -- Periodicals; Pigments -- Periodicals; 667.2
• DOI: 10.1016/j.dyepig.2020.108861
• Languages: English
• ISSNs: 0143-7208

Abstract

Abstract: Two new 4-OH coumarin based rotary switches, containing fixed carbonyl groups in the rotor, have been synthesized and their properties have been studied by combined use of DFT calculations and molecular spectroscopy (UV–Vis absorbance and emission, NMR). It was found that the structure of the stator (naphthyl in 2 or quinolyl moiety in 3 ) and solvents polarity do not influence their azo-hydrazone tautomerism. Both compounds exist as keto (hydrazone) tautomers. The NMR data indicate a mixture of E (major) and Z (minor) keto form isomers in solution. The results are in very good agreement with ground state DFT calculations. The keto tautomers exhibit different emission behavior depending on the structure of the stators. Comparing to 2, more intensive emission and higher lifetime was observed in 3, where the formation of intramolecular hydrogen bonding of the hydrazone NH with the N atom of quinoline restricts the rotation of the stator. According to the spectral data and the TDDFT analysis the observed emission originates from the excitation of the keto tautomers and does not include excited state proton transfer. It was shown that the protonation is a suitable stimulus for E / Z switching in 2, where a possible mechanism is sketched. In the case of 3, the addition of acid leads to the protonation of the quinolyl nitrogen atom, which slightly affects the E / Z isomerization ratio. Graphical abstract: Image 1 Highlights: New 4-OH coumarin based rotary switches, containing fixed carbonyl groups in the rotor, are designed. The structure of the stator and solvents polarity do not influence their azo-hydrazone tautomerism. The compounds exist as E and Z isomers of the hydrazone tautomer. The observed emission originates from the excited keto tautomers and excludes excited state proton transfer. The protonation is a suitable stimulus for E / Z switching.