Stabilization of Pancake Bonding in (TCNQ)2.− Dimers in the Radical‐Anionic Salt (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN) Solvate and Antiferromagnetism Induction
Abstract We report a new antiferromagnetic radical‐anion salt (RAS) formed from 7,7,8,8‐tetracyanquinonedimethane (TCNQ) anion and 2‐amino‐5‐chloro‐pyridine cation with the composition of (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN). The crystallographic data indicates the formation of (TCNQ)2.− radical‐anion...
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2019-07-01
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| Series: | ChemistryOpen |
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| Online Access: | https://doi.org/10.1002/open.201900179 |
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| author | Dr. Tetiana N. Starodub Dr. Erik Čižmár Andrii Kliuikov Prof. Vladimir A. Starodub Prof. Alexander Feher Dr. Mariana Kozlowska |
| author_facet | Dr. Tetiana N. Starodub Dr. Erik Čižmár Andrii Kliuikov Prof. Vladimir A. Starodub Prof. Alexander Feher Dr. Mariana Kozlowska |
| author_sort | Dr. Tetiana N. Starodub |
| collection | DOAJ |
| description | Abstract We report a new antiferromagnetic radical‐anion salt (RAS) formed from 7,7,8,8‐tetracyanquinonedimethane (TCNQ) anion and 2‐amino‐5‐chloro‐pyridine cation with the composition of (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN). The crystallographic data indicates the formation of (TCNQ)2.− radical‐anion π‐dimers in the synthesized RAS. Unrestricted density functional theory calculations show that the formed π‐dimers characterize with strong π‐stacking “pancake” interactions, resulting in high electronic coupling, enabling efficient charge transfer properties, but π‐dimers cannot be stable in the isolated conditions as a result of strong Coulomb repulsions. In a crystal, where (TCNQ)2.− π‐dimers bound in the endless chainlets via supramolecular bonds with (N−CH3−2‐NH2−5‐Cl−Py)+ cations, the repulsion forces are screened, allowing for specific parallel π‐stacking interactions and stable radical‐anion dimers formation. Measurements of magnetic susceptibility and magnetization confirm antiferromagnetic properties of RAS, what is in line with the higher stability of ground singlet state of the radical‐anion pair, calculated by means of the DFT. Therefore, the reported radical‐anion (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN) solvate has promising applications in novel magnetics with supramolecular structures. |
| first_indexed | 2024-12-21T16:37:10Z |
| format | Article |
| id | doaj.art-ce9954cd97b74c8cb58ef775d036d4bb |
| institution | Directory Open Access Journal |
| issn | 2191-1363 |
| language | English |
| last_indexed | 2024-12-21T16:37:10Z |
| publishDate | 2019-07-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemistryOpen |
| spelling | doaj.art-ce9954cd97b74c8cb58ef775d036d4bb2022-12-21T18:57:11ZengWiley-VCHChemistryOpen2191-13632019-07-018798498810.1002/open.201900179Stabilization of Pancake Bonding in (TCNQ)2.− Dimers in the Radical‐Anionic Salt (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN) Solvate and Antiferromagnetism InductionDr. Tetiana N. Starodub0Dr. Erik Čižmár1Andrii Kliuikov2Prof. Vladimir A. Starodub3Prof. Alexander Feher4Dr. Mariana Kozlowska5Institute of Chemistry Jan Kochanowski University 25-405 Kielce PolandInstitute of Physics, Faculty of Science P. J. Šafárik University Park Angelinum 9 041 54 Košice SlovakiaInstitute of Physics, Faculty of Science P. J. Šafárik University Park Angelinum 9 041 54 Košice SlovakiaInstitute of Chemistry Jan Kochanowski University 25-405 Kielce PolandInstitute of Physics, Faculty of Science P. J. Šafárik University Park Angelinum 9 041 54 Košice SlovakiaInstitute of Nanotechnology (INT) Karlsruhe Institute of Technology (KIT) 76344 Eggenstein-Leopoldshafen GermanyAbstract We report a new antiferromagnetic radical‐anion salt (RAS) formed from 7,7,8,8‐tetracyanquinonedimethane (TCNQ) anion and 2‐amino‐5‐chloro‐pyridine cation with the composition of (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN). The crystallographic data indicates the formation of (TCNQ)2.− radical‐anion π‐dimers in the synthesized RAS. Unrestricted density functional theory calculations show that the formed π‐dimers characterize with strong π‐stacking “pancake” interactions, resulting in high electronic coupling, enabling efficient charge transfer properties, but π‐dimers cannot be stable in the isolated conditions as a result of strong Coulomb repulsions. In a crystal, where (TCNQ)2.− π‐dimers bound in the endless chainlets via supramolecular bonds with (N−CH3−2‐NH2−5‐Cl−Py)+ cations, the repulsion forces are screened, allowing for specific parallel π‐stacking interactions and stable radical‐anion dimers formation. Measurements of magnetic susceptibility and magnetization confirm antiferromagnetic properties of RAS, what is in line with the higher stability of ground singlet state of the radical‐anion pair, calculated by means of the DFT. Therefore, the reported radical‐anion (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN) solvate has promising applications in novel magnetics with supramolecular structures.https://doi.org/10.1002/open.201900179charge transfer processescrystal engineeringdensity functional calculationsmagnetic propertiesradical ions |
| spellingShingle | Dr. Tetiana N. Starodub Dr. Erik Čižmár Andrii Kliuikov Prof. Vladimir A. Starodub Prof. Alexander Feher Dr. Mariana Kozlowska Stabilization of Pancake Bonding in (TCNQ)2.− Dimers in the Radical‐Anionic Salt (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN) Solvate and Antiferromagnetism Induction ChemistryOpen charge transfer processes crystal engineering density functional calculations magnetic properties radical ions |
| title | Stabilization of Pancake Bonding in (TCNQ)2.− Dimers in the Radical‐Anionic Salt (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN) Solvate and Antiferromagnetism Induction |
| title_full | Stabilization of Pancake Bonding in (TCNQ)2.− Dimers in the Radical‐Anionic Salt (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN) Solvate and Antiferromagnetism Induction |
| title_fullStr | Stabilization of Pancake Bonding in (TCNQ)2.− Dimers in the Radical‐Anionic Salt (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN) Solvate and Antiferromagnetism Induction |
| title_full_unstemmed | Stabilization of Pancake Bonding in (TCNQ)2.− Dimers in the Radical‐Anionic Salt (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN) Solvate and Antiferromagnetism Induction |
| title_short | Stabilization of Pancake Bonding in (TCNQ)2.− Dimers in the Radical‐Anionic Salt (N−CH3−2‐NH2−5Cl−Py)(TCNQ)(CH3CN) Solvate and Antiferromagnetism Induction |
| title_sort | stabilization of pancake bonding in tcnq 2 dimers in the radical anionic salt n ch3 2 nh2 5cl py tcnq ch3cn solvate and antiferromagnetism induction |
| topic | charge transfer processes crystal engineering density functional calculations magnetic properties radical ions |
| url | https://doi.org/10.1002/open.201900179 |
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