R. Vulcano, P. Pengo, S. Velari, J. Wouters, A. De Vita, P. Tecilla, D. Bonifazi
J. Am. Chem. Soc., 2017, 139, 50, 18271-18280
The E/Z isomerization process of a uracil-azobenzene derivative in which the nucleobase is conjugated to a phenyldiazene tail is studied in view of its ability to form triply-H-bonded complexes with a suitably complementary 2,6-diacetylamino-4-pyridine ligand. UV-Vis and 1H-NMR investigations of the photochemical and thermal isomerization kinetics show that the thermal Z→E interconversion is four-fold accelerated upon formation of the H-bonded complex. DFT calculations show that the formation of triple H-bonds triggers a significant elongation of the N=N double bond, caused by an increase of its πg∗ antibonding character. This results in a reduction of the N=N torsional barrier and thus in accelerated thermal Z→E isomerization. Combined with light controlled E→Z isomerization this enables controllable fractional tuning of the two configurational isomers.