Azo-hydrazone molecular switches: Synthesis and NMR conformational investigation

Atanas Kurutos*, Fadhil S. Kamounah, Georgi M. Dobrikov, Michael Pittelkow, Stephan P. A. Sauer, Poul Erik Hansen

*Corresponding author

Publikation: Bidrag til tidsskriftTidsskriftartikelpeer review

Abstract

A series of five intramolecularly hydrogen-bonded arylhydrazone (aryl = phenol, p-nitrophenol, anisole, quinoline) derived molecular switches have been synthesized and characterized by NMR and HRMS techniques. It was found that the compounds exist as different isomers in solution. An investigation of both conformational and/or configurational changes of the azo-hydrazone compounds was carried out by 1D 1 H- and 13 C- spectra, 2D NOESY, COSY, HSQC, and HMBC techniques. It was found that these stimuli-responsive molecular switches exist mainly in the E form by intramolecularly hydrogen bonded between NH and the pyridine nitrogen at equilibrium. Deprotonation of the neutral E form yields the E' deprotonated isomer. Prediction of 13 C-NMR chemical shifts was achieved by DFT quantum mechanical calculations. Anions have traditionally been difficult to calculate correctly, so calculations of the anion using different functionals, basis sets, and solvent effects are also included. Deuterium isotope effects on the 13 C-NMR chemical shifts were employed in the assignments and furthermore utilized as indicators of intramolecular hydrogen bonding. Studies in various organic solvents including CDCl3 , CD3 CN, and DMSO-d6 were also performed aiming to monitor dynamic changes over several days. The effect of the hydrogen bonded solvents leads to Z forms.

OriginalsprogEngelsk
TidsskriftMagnetic Resonance in Chemistry
Vol/bind59
Udgave nummer11
Sider (fra-til)1116-1125
Antal sider10
ISSN0749-1581
DOI
StatusUdgivet - 1 nov. 2021

Emneord

  • 13C-NMR
  • 1H-NMR
  • 2D-NMR
  • azo-dyes
  • isotope effect
  • molecular switches

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