Non-Innocent Base Properties of 3- and 4-Pyridyl-dithia- and Diselenadiazolyl Radicals : The Effect of N-Methylation
Taponen, A., Wong, J. W. L., Lekin, K., Assoud, A., Robertson, C. M., Lahtinen, M., Clérac, R., Tuononen, H., Mailman, A., & Oakley, R. T. (2018). Non-Innocent Base Properties of 3- and 4-Pyridyl-dithia- and Diselenadiazolyl Radicals : The Effect of N-Methylation. Inorganic Chemistry, 57(21), 13901-13911. https://doi.org/10.1021/acs.inorgchem.8b02416
Julkaistu sarjassa
Inorganic ChemistryTekijät
Päivämäärä
2018Tekijänoikeudet
© 2018 American Chemical Society
Condensation of persilylated nicotinimideamide and isonicotinimideamide with sulfur monochloride affords double salts of the 3-, 4-pyridyl-substituted 1,2,3,5-dithiadiazolylium DTDA cations of the general formula [3-, 4-pyDTDA][Cl][HCl] in which the pyridyl nitrogen serves as a noninnocent base. Reduction of these salts with triphenylantimony followed by deprotonation of the intermediate-protonated radical affords the free base radicals [3-, 4-pyDTDA], the crystal structures of which, along with those of their diselenadiazolyl analogues [3-, 4-pyDSDA], have been characterized by powder or single-crystal X-ray diffraction. The crystal structures consist of “pancake” π-dimers linked head-to-tail into ribbonlike arrays by η2-S2---N(py) intermolecular secondary bonding interactions. Methylation of the persilylated (iso)nicotinimide-amides prior to condensation with sulfur monochloride leads to N-methylated double chloride salts Me[3-, 4-pyDTDA][Cl]2, which can be converted by metathesis into the corresponding triflates Me[3-, 4-pyDTDA][OTf]2 and then reduced to the N-methylated radical triflates Me[3-, 4-pyDTDA][OTf]. The crystal structures of both the N-methylated double triflate and radical triflate salts have been determined by single-crystal X-ray diffraction. The latter consist of trans-cofacial π-dimers strongly ion-paired with triflate anions. Variable temperature magnetic susceptibility measurements on both the neutral and radical ion dimers indicate that they are diamagnetic over the temperature range 2–300 K.
...
Julkaisija
American Chemical SocietyISSN Hae Julkaisufoorumista
0020-1669Asiasanat
Julkaisu tutkimustietojärjestelmässä
https://converis.jyu.fi/converis/portal/detail/Publication/28665896
Metadata
Näytä kaikki kuvailutiedotKokoelmat
Rahoittaja(t)
Euroopan komissio; Suomen AkatemiaRahoitusohjelmat(t)
MSCA Marie Skłodowska-Curie Actions, H2020; Akatemiahanke, SA
The content of the publication reflects only the author’s view. The funder is not responsible for any use that may be made of the information it contains.
Lisätietoja rahoituksesta
This work was supported by the Natural Sciences and Engineering Research Council of Canada (NSERCC), the University of Jyväskylä, the Academy of Finland (projects 253907 and 289172), the European Union’s H2020 research and innovations programme (under the Marie Skłodowska-Curie Grant Agreement 659123), CNRS, the University of Bordeaux, the Région Nouvelle Aquitaine, the GdR MCM-2, and the MOLSPIN COST action CA15128. We thank the Diamond Light Source for access to beamlines I11 and I19. ...Lisenssi
Samankaltainen aineisto
Näytetään aineistoja, joilla on samankaltainen nimeke tai asiasanat.
-
Polymorphism in a π stacked Blatter radical : structures and magnetic properties of 3-(phenyl)-1-(pyrid-2-yl)-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl
Constantinides, Christos P.; Lawson, Daniel B.; Zissimou, Georgia A.; Berezin, Andrey A.; Mailman, Aaron; Manoli, Maria; Kourtellaris, Andreas; Leitus, Gregory M.; Clérac, Rodolphe; Tuononen, Heikki M.; Koutentis, Panayiotis A. (Royal Society of Chemistry, 2020)3-(Phenyl)-1-(pyrid-2-yl)-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl (2) demonstrates the first example of polymorphism in the family of Blatter radicals. Two polymorphs, 2α and 2β, have been identified and characterized by ... -
Substituent effects on exchange anisotropy in single- and multiorbital organic radical magnets
Marbey, Jonathan; Mailman, Aaron; Oakley, Richard, T.; Hill, Stephen; Winter, Stephen, M. (American Physical Society (APS), 2024)The contribution of heavy-atom substituents to the overall spin-orbit interaction in two classes of organic radical molecular magnets is discussed. In “single-orbital” radicals, spin-orbit coupling (SOC) effects are well ... -
The Role of Orbital Symmetries in Enforcing Ferromagnetic Ground State in Mixed Radical Dimers
Mansikkamäki, Akseli; Tuononen, Heikki (American Chemical Society, 2018)One of the first steps in designing ferromagnetic (FM) molecular materials of p-block radicals is the suppression of covalent radical–radical interactions that stabilize a diamagnetic ground state. In this contribution, ... -
Toxicological and bioactivity evaluation of blackcurrant press cake, sea buckthorn leaves and bark from Scots pine and Norway spruce extracts under a green integrated approach
Pap, Nora; Reshamwala, Dhanik; Korpinen, Risto; Kilpeläinen, Petri; Fidelis, Marina; Furtado, Marianna M.; Sant’Ana, Anderson S.; Wen, Mingchun; Zhang, Liang; Hellström, Jarkko; Marnilla, Pertti; Mattila, Pirjo; Sarjala, Tytti; Yang, Baoru; dos Santos Lima, Amanda; Azevedo, Luciana; Marjomäki, Varpu; Granato, Daniel (Elsevier, 2021)Aqueous extracts from blackcurrant press cake (BC), Norway spruce bark (NS), Scots pine bark (SP), and sea buckthorn leaves (SB) were obtained using maceration and pressurized hot water and tested for their bioactivities. ... -
A Novel Halogen Bond Acceptor : 1-(4-Pyridyl)-4-Thiopyridine (PTP) Zwitterion
Ding, Xin; Tuikka, Matti; Haukka, Matti (MDPI, 2020)Sulfur is a widely used halogen bond (XB) acceptor, but only a limited number of neutral XB acceptors with bifurcated sp3-S sites have been reported. In this work a new bidentate XB acceptor, 1-(4-pyridyl)-4-thiopyridine ...
Ellei toisin mainittu, julkisesti saatavilla olevia JYX-metatietoja (poislukien tiivistelmät) saa vapaasti uudelleenkäyttää CC0-lisenssillä.