Azo-hydrazone molecular switches: Synthesis and NMR conformational investigation
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Azo-hydrazone molecular switches : Synthesis and NMR conformational investigation. / Kurutos, Atanas; Kamounah, Fadhil S.; Dobrikov, Georgi M.; Pittelkow, Michael; Sauer, Stephan P. A.; Hansen, Poul Erik.
I: Magnetic Resonance in Chemistry, Bind 59, Nr. 11, 04.10.2021, s. 1116-1125.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Azo-hydrazone molecular switches
T2 - Synthesis and NMR conformational investigation
AU - Kurutos, Atanas
AU - Kamounah, Fadhil S.
AU - Dobrikov, Georgi M.
AU - Pittelkow, Michael
AU - Sauer, Stephan P. A.
AU - Hansen, Poul Erik
PY - 2021/10/4
Y1 - 2021/10/4
N2 - 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 1H- and 13C- 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 13C-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 13C-NMR chemical shifts was employed in the assignments and furthermore utilized as indicators of intramolecular hydrogen bonding. Studies in various organic solvents including CDCl3, CD3CN 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.
AB - 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 1H- and 13C- 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 13C-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 13C-NMR chemical shifts was employed in the assignments and furthermore utilized as indicators of intramolecular hydrogen bonding. Studies in various organic solvents including CDCl3, CD3CN 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.
KW - Faculty of Science
KW - azo-dyes
KW - Molecular switches
KW - isotope effect
KW - 1H-NMR
KW - 13C-NMR
KW - 2D-NMR
KW - DFT
KW - Density functional theory
KW - computational chemistry
U2 - 10.1002/mrc.5164
DO - 10.1002/mrc.5164
M3 - Journal article
C2 - 33860564
VL - 59
SP - 1116
EP - 1125
JO - Magnetic Resonance in Chemistry
JF - Magnetic Resonance in Chemistry
SN - 0030-4921
IS - 11
ER -
ID: 259724199