65447-26-9Relevant academic research and scientific papers
Platform for High-Spin Molecules: A Verdazyl-Nitronyl Nitroxide Triradical with Quartet Ground State
Bagryanskaya, Irina Yu.,Bogomyakov, Artem S.,Fedin, Matvey V.,Gorbunov, Dmitry E.,Gritsan, Nina P.,Kazantsev, Maxim S.,Ovcharenko, Victor I.,Petunin, Pavel V.,Postnikov, Pavel S.,Samoilova, Rimma I.,Shundrina, Inna K.,Stass, Dmitri V.,Tretyakov, Evgeny V.,Trusova, Marina E.,Zhivetyeva, Svetlana I.
, p. 8164 - 8176 (2021)
Thermally resistant air-stable organic triradicals with a quartet ground state and a large energy gap between spin states are still unique compounds. In this work, we succeeded to design and prepare the first highly stable triradical, consisting of oxoverdazyl and nitronyl nitroxide radical fragments, with a quartet ground state. The triradical and its diradical precursor were synthesized via a palladium-catalyzed cross-coupling reaction of diiodoverdazyl with nitronyl nitroxide-2-ide gold(I) complex. Both paramagnetic compounds were fully characterized by single-crystal X-ray diffraction analysis, superconducting quantum interference device magnetometry, EPR spectroscopy in various matrices, and cyclic voltammetry. In the diradical, the verdazyl and nitronyl nitroxide centers demonstrated full reversibility of redox process, while for the triradical, the electrochemical reduction and oxidation proceed at practically the same redox potentials, but become quasi-reversible. A series of high-level CASSCF/NEVPT2 calculations was performed to predict inter- and intramolecular exchange interactions in crystals of di- and triradicals and to establish their magnetic motifs. Based on the predicted magnetic motifs, the temperature dependences of the magnetic susceptibility were analyzed, and the singlet-triplet (135 ± 10 cm-1) and doublet-quartet (17 ± 2 and 152 ± 19 cm-1) splitting was found to be moderate. Unique high stability of synthesized verdazyl-nitronylnitroxide triradical opens new perspectives for further functionalization and design of high-spin systems with four or more spins.
The syntheses, structures and spectroelectrochemical properties of 6-oxo-verdazyl derivatives bearing surface anchoring groups
Cox, Nicholas,Judd, Martyna,Korb, Marcus,Kumar, Varshini J.,Low, Paul J.,Moggach, Stephen A.,Rousset, Elodie,Wu, Jian-Zhong
, p. 1896 - 1915 (2022/02/17)
A series of 6-oxo-verdazyl radicals functionalised at the 1-and 5-positions by tolyl, thioanisole and iodophenyl groups were synthesised using conventional strategies. Facile Sonogashira cross-coupling reactions of terminal alkynes with the diiodo derivat
sp2-C–H Acetoxylation of Diversely Substituted (E)-1-(Arylmethylene)-2-phenylhydrazines Using PhI(OAc)2 as Acetoxy Source at Ambient Conditions
Brahmachari, Goutam,Karmakar, Indrajit
supporting information, p. 5925 - 5933 (2019/08/16)
A catalyst- and additive-free simple and straightforward method for regioselective direct sp2 C–H acetoxylation reaction of aldehyde hydrazones has been achieved at ambient temperature employing PIDA as an acetoxy source. The scope of the reaction has been successfully verified with a wide range of biologically important aldehyde hydrazones with diverse functional group tolerance. The method is highly selective, mild and efficient, operationally simple, rapid and high-yielding.
Functional group transformations in derivatives of 1,4-dihydrobenzo[1,2,4] triazinyl radical
Bodzioch, Agnieszka,Zheng, Minyan,Kaszyński, Piotr,Utecht, Greta
, p. 7294 - 7310 (2014/09/16)
Transformations of functional groups OCOPh, OCH2Ph, I, NO 2, and CO2Me in Blatter's radical derivatives 1-5 were investigated in order to develop synthetic tools for incorporation of the benzo[1,2,4]triazinyl system into c
