Bis(2,6-pyrazolyl)pyridines as a New Scaffold for Coordination Polymers
Two coordination polymers, Fe(L<sup>OBF</sup><sub>3</sub>)(CH<sub>3</sub>COO)(CH<sub>3</sub>CN)<sub>2</sub>]<sub>n</sub>•nCH<sub>3</sub>CN and [Fe(L<sup>O−</sup>)<sub>2</sub>AgNO<sub>3&l...
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MDPI AG
2023-05-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/11/4275 |
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| author | Igor A. Nikovskiy Pavel V. Dorovatovskii Valentin V. Novikov Yulia V. Nelyubina |
| author_facet | Igor A. Nikovskiy Pavel V. Dorovatovskii Valentin V. Novikov Yulia V. Nelyubina |
| author_sort | Igor A. Nikovskiy |
| collection | DOAJ |
| description | Two coordination polymers, Fe(L<sup>OBF</sup><sub>3</sub>)(CH<sub>3</sub>COO)(CH<sub>3</sub>CN)<sub>2</sub>]<sub>n</sub>•nCH<sub>3</sub>CN and [Fe(L<sup>O−</sup>)<sub>2</sub>AgNO<sub>3</sub>BF<sub>4</sub>•CH<sub>3</sub>OH]<sub>n</sub>•1.75nCH<sub>3</sub>OH•nH<sub>2</sub>O (L<sup>O−</sup> = 3,3′-(4-(4-cyanophenyl)pyridine-2,6-diyl)bis(1-(2,6-dichlorophenyl)-1H-pyrazol-5-olate)), were obtained via a PCET-assisted process that uses the hydroxy-pyrazolyl moiety of the ligand and the iron(II) ion as sources of proton and electron, respectively. Our attempts to produce heterometallic compounds under mild conditions of reactant diffusion resulted in the first coordination polymer of 2,6-bis(pyrazol-3-yl)pyridines to retain the core N<sub>3</sub>(L)MN<sub>3</sub>(L). Under harsh solvothermal conditions, a hydrogen atom transfer to the tetrafluoroborate anion caused the transformation of the hydroxyl groups into OBF<sub>3</sub> in the third coordination polymer of 2,6-bis(pyrazol-3-yl)pyridines. This PCET-assisted approach may be applicable to produce coordination polymers and metal–organic frameworks with the SCO-active core N<sub>3</sub>(L)MN<sub>3</sub>(L) formed by pyrazolone- and other hydroxy-pyridine-based ligands. |
| first_indexed | 2024-03-11T03:01:40Z |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T03:01:40Z |
| publishDate | 2023-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-6c47ba3aa20f46e3bd79554c3028dde02023-11-18T08:14:23ZengMDPI AGMolecules1420-30492023-05-012811427510.3390/molecules28114275Bis(2,6-pyrazolyl)pyridines as a New Scaffold for Coordination PolymersIgor A. Nikovskiy0Pavel V. Dorovatovskii1Valentin V. Novikov2Yulia V. Nelyubina3Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Street 28, 119991 Moscow, RussiaNational Research Centre “Kurchatov Institute”, Akademika Kurchatova pl. 1, 123182 Moscow, RussiaMoscow Institute of Physics and Technology, National Research University, Institutskiy per. 9, 141700 Dolgoprudny, RussiaNesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Street 28, 119991 Moscow, RussiaTwo coordination polymers, Fe(L<sup>OBF</sup><sub>3</sub>)(CH<sub>3</sub>COO)(CH<sub>3</sub>CN)<sub>2</sub>]<sub>n</sub>•nCH<sub>3</sub>CN and [Fe(L<sup>O−</sup>)<sub>2</sub>AgNO<sub>3</sub>BF<sub>4</sub>•CH<sub>3</sub>OH]<sub>n</sub>•1.75nCH<sub>3</sub>OH•nH<sub>2</sub>O (L<sup>O−</sup> = 3,3′-(4-(4-cyanophenyl)pyridine-2,6-diyl)bis(1-(2,6-dichlorophenyl)-1H-pyrazol-5-olate)), were obtained via a PCET-assisted process that uses the hydroxy-pyrazolyl moiety of the ligand and the iron(II) ion as sources of proton and electron, respectively. Our attempts to produce heterometallic compounds under mild conditions of reactant diffusion resulted in the first coordination polymer of 2,6-bis(pyrazol-3-yl)pyridines to retain the core N<sub>3</sub>(L)MN<sub>3</sub>(L). Under harsh solvothermal conditions, a hydrogen atom transfer to the tetrafluoroborate anion caused the transformation of the hydroxyl groups into OBF<sub>3</sub> in the third coordination polymer of 2,6-bis(pyrazol-3-yl)pyridines. This PCET-assisted approach may be applicable to produce coordination polymers and metal–organic frameworks with the SCO-active core N<sub>3</sub>(L)MN<sub>3</sub>(L) formed by pyrazolone- and other hydroxy-pyridine-based ligands.https://www.mdpi.com/1420-3049/28/11/42752,6-bis(pyrazol-3-yl)pyridinecoordination polymermolecular designproton-coupled electron transferspin crossover |
| spellingShingle | Igor A. Nikovskiy Pavel V. Dorovatovskii Valentin V. Novikov Yulia V. Nelyubina Bis(2,6-pyrazolyl)pyridines as a New Scaffold for Coordination Polymers Molecules 2,6-bis(pyrazol-3-yl)pyridine coordination polymer molecular design proton-coupled electron transfer spin crossover |
| title | Bis(2,6-pyrazolyl)pyridines as a New Scaffold for Coordination Polymers |
| title_full | Bis(2,6-pyrazolyl)pyridines as a New Scaffold for Coordination Polymers |
| title_fullStr | Bis(2,6-pyrazolyl)pyridines as a New Scaffold for Coordination Polymers |
| title_full_unstemmed | Bis(2,6-pyrazolyl)pyridines as a New Scaffold for Coordination Polymers |
| title_short | Bis(2,6-pyrazolyl)pyridines as a New Scaffold for Coordination Polymers |
| title_sort | bis 2 6 pyrazolyl pyridines as a new scaffold for coordination polymers |
| topic | 2,6-bis(pyrazol-3-yl)pyridine coordination polymer molecular design proton-coupled electron transfer spin crossover |
| url | https://www.mdpi.com/1420-3049/28/11/4275 |
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