Abstract
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 4-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 NN double bond, caused by an increase of its g∗ antibonding character. This results in a reduction of the NN 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.
Original language | English |
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Pages (from-to) | 18271-18280 |
Number of pages | 10 |
Journal | Journal of the American Chemical Society |
Volume | 139 |
Issue number | 50 |
DOIs | |
Publication status | Published - 20 Dec 2017 |
Funding
D.B. gratefully acknowledges the Science Policy Office of the Belgian Federal Government (BELSPO-IAP 7/05 project) and the EU through the ERC COLORLAND project. P.T. and D.B. thank the HORIZON2020 Marie Sklodowska Curie Actions through the INFUSION project. R.V. thanks UNamur for her doctoral and teaching assistant position. We thank UNamur for the physical chemistry and characterization (PC2) and Bernadette Norberg for the X-ray measurements and data interpretation. We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194//1). A.D.V. acknowledges funding from the European Union's Horizon 2020 research and innovation program (Grant No. 676580, The NOMAD Laboratory, a European Centre of Excellence).
Funders | Funder number |
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Horizon 2020 Framework Programme | 734834 |
European Resuscitation Council | |
Engineering and Physical Sciences Research Council | EP/P020194//1 |
European External Action Service | |
Horizon 2020 | 676580 |
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High Performance Computing Technology Platform
Champagne, B. (Manager)
Technological Platform High Performance ComputingFacility/equipment: Technological Platform
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Physical Chemistry and characterization(PC2)
Wouters, J. (Manager), Aprile, C. (Manager) & Fusaro, L. (Manager)
Technological Platform Physical Chemistry and characterizationFacility/equipment: Technological Platform
Datasets
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CCDC 1435199: Experimental Crystal Structure Determination
Vulcano, R. (Contributor), Pengo, P. (Creator), Velari, S. (Creator), Wouters, J. (Contributor), De Vita, A. (Creator), Tecilla, P. (Creator) & Bonifazi, D. (Contributor), University of Namur, 20 Dec 2017
DOI: 10.5517/ccdc.csd.cc1k5frx, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1k5frx&sid=DataCite
Dataset
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CCDC 1474613: Experimental Crystal Structure Determination
Vulcano, R. (Contributor), Pengo, P. (Creator), Velari, S. (Creator), Wouters, J. (Contributor), De Vita, A. (Creator), Tecilla, P. (Creator) & Bonifazi, D. (Contributor), University of Namur, 20 Dec 2017
DOI: 10.5517/ccdc.csd.cc1lhg5q, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lhg5q&sid=DataCite
Dataset
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CCDC 1435201: Experimental Crystal Structure Determination
Vulcano, R. (Contributor), Pengo, P. (Creator), Velari, S. (Creator), Wouters, J. (Contributor), De Vita, A. (Creator), Tecilla, P. (Creator) & Bonifazi, D. (Contributor), University of Namur, 20 Dec 2017
DOI: 10.5517/ccdc.csd.cc1k5ftz, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1k5ftz&sid=DataCite
Dataset