Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica
The chemical immobilization of cobalt(II) ions in a silica aerogel matrix enabled the synthesis of the first representative example of aerogel-based single-ion magnets. For the synthesis of the lyogels, methyl-trimethoxysilane and N-3-(trimethoxysilyl)propyl ethylenediamine were co-hydrolyzed, then...
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MDPI AG
2023-01-01
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| Online Access: | https://www.mdpi.com/1420-3049/28/1/418 |
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| author | Sergey Yu. Kottsov Maxim A. Shmelev Alexander E. Baranchikov Mikhail A. Kiskin Alim U. Sharipov Nikolay N. Efimov Irina K. Rubtsova Stanislav A. Nikolaevskii Gennady P. Kopitsa Tamara V. Khamova Ilya V. Roslyakov Igor L. Eremenko Vladimir K. Ivanov |
| author_facet | Sergey Yu. Kottsov Maxim A. Shmelev Alexander E. Baranchikov Mikhail A. Kiskin Alim U. Sharipov Nikolay N. Efimov Irina K. Rubtsova Stanislav A. Nikolaevskii Gennady P. Kopitsa Tamara V. Khamova Ilya V. Roslyakov Igor L. Eremenko Vladimir K. Ivanov |
| author_sort | Sergey Yu. Kottsov |
| collection | DOAJ |
| description | The chemical immobilization of cobalt(II) ions in a silica aerogel matrix enabled the synthesis of the first representative example of aerogel-based single-ion magnets. For the synthesis of the lyogels, methyl-trimethoxysilane and N-3-(trimethoxysilyl)propyl ethylenediamine were co-hydrolyzed, then the ethylenediamine groups that were immobilized on the silica matrix enabled the subsequent binding of cobalt(II) ions. Lyogels with various amounts of ethylenediamine moieties (0.1–15 mol %) were soaked in isopropanol solutions of cobalt(II) nitrate and further supercritically dried in carbon dioxide to obtain aerogels with a specific surface area of 210–596 m<sup>2</sup>·g<sup>−1</sup>, an apparent density of 0.403–0.740 cm<sup>3</sup>·g<sup>−1</sup> and a porosity of 60–78%. The actual cobalt content in the aerogels was 0.01–1.50 mmol per 1 g of SiO<sub>2</sub>, which could easily be tuned by the concentration of ethylenediamine moieties in the silica matrix. The introduction of cobalt(II) ions into the ethylenediamine-modified silica aerogel promoted the stability of the diamine moieties at the supercritical drying stage. The molecular prototype of the immobilized cobalt(II) complex, bearing one ethylenediamine ligand [Co(en)(MeCN)(NO<sub>3</sub>)<sub>2</sub>], was synthesized and structurally characterized. Using magnetometry in the DC mode, it was shown that cobalt(II)-modified silica aerogels exhibited slow magnetic relaxation in a nonzero field. A decrease in cobalt(II) concentration in aerogels from 1.5 mmol to 0.14 mmol per 1 g of SiO<sub>2</sub> resulted in a weakening of inter-ion interactions; the magnetization reversal energy barrier likewise increased from 4 to 18 K. |
| first_indexed | 2024-03-09T03:29:05Z |
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| id | doaj.art-0701f9b8ff734ea59f9043e17f979d72 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T03:29:05Z |
| publishDate | 2023-01-01 |
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| series | Molecules |
| spelling | doaj.art-0701f9b8ff734ea59f9043e17f979d722023-12-03T14:57:59ZengMDPI AGMolecules1420-30492023-01-0128141810.3390/molecules28010418Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in SilicaSergey Yu. Kottsov0Maxim A. Shmelev1Alexander E. Baranchikov2Mikhail A. Kiskin3Alim U. Sharipov4Nikolay N. Efimov5Irina K. Rubtsova6Stanislav A. Nikolaevskii7Gennady P. Kopitsa8Tamara V. Khamova9Ilya V. Roslyakov10Igor L. Eremenko11Vladimir K. Ivanov12Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, RussiaKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, RussiaKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, RussiaKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, RussiaKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, RussiaKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, RussiaKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, RussiaKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, RussiaSt.-Petersburg Nuclear Physics Institute, National Research Center “Kurchatov Institute”, Gatchina 188300, RussiaGrebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, St.-Petersburg 199034, RussiaKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, RussiaKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, RussiaKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, RussiaThe chemical immobilization of cobalt(II) ions in a silica aerogel matrix enabled the synthesis of the first representative example of aerogel-based single-ion magnets. For the synthesis of the lyogels, methyl-trimethoxysilane and N-3-(trimethoxysilyl)propyl ethylenediamine were co-hydrolyzed, then the ethylenediamine groups that were immobilized on the silica matrix enabled the subsequent binding of cobalt(II) ions. Lyogels with various amounts of ethylenediamine moieties (0.1–15 mol %) were soaked in isopropanol solutions of cobalt(II) nitrate and further supercritically dried in carbon dioxide to obtain aerogels with a specific surface area of 210–596 m<sup>2</sup>·g<sup>−1</sup>, an apparent density of 0.403–0.740 cm<sup>3</sup>·g<sup>−1</sup> and a porosity of 60–78%. The actual cobalt content in the aerogels was 0.01–1.50 mmol per 1 g of SiO<sub>2</sub>, which could easily be tuned by the concentration of ethylenediamine moieties in the silica matrix. The introduction of cobalt(II) ions into the ethylenediamine-modified silica aerogel promoted the stability of the diamine moieties at the supercritical drying stage. The molecular prototype of the immobilized cobalt(II) complex, bearing one ethylenediamine ligand [Co(en)(MeCN)(NO<sub>3</sub>)<sub>2</sub>], was synthesized and structurally characterized. Using magnetometry in the DC mode, it was shown that cobalt(II)-modified silica aerogels exhibited slow magnetic relaxation in a nonzero field. A decrease in cobalt(II) concentration in aerogels from 1.5 mmol to 0.14 mmol per 1 g of SiO<sub>2</sub> resulted in a weakening of inter-ion interactions; the magnetization reversal energy barrier likewise increased from 4 to 18 K.https://www.mdpi.com/1420-3049/28/1/418magnetic propertiesaerogelchemical immobilizationN-3-(trimethoxysilyl)propyl ethylenediaminesingle-ion magnetsingle-molecule magnet |
| spellingShingle | Sergey Yu. Kottsov Maxim A. Shmelev Alexander E. Baranchikov Mikhail A. Kiskin Alim U. Sharipov Nikolay N. Efimov Irina K. Rubtsova Stanislav A. Nikolaevskii Gennady P. Kopitsa Tamara V. Khamova Ilya V. Roslyakov Igor L. Eremenko Vladimir K. Ivanov Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica Molecules magnetic properties aerogel chemical immobilization N-3-(trimethoxysilyl)propyl ethylenediamine single-ion magnet single-molecule magnet |
| title | Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica |
| title_full | Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica |
| title_fullStr | Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica |
| title_full_unstemmed | Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica |
| title_short | Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica |
| title_sort | aerogel based single ion magnets a case study of a cobalt ii complex immobilized in silica |
| topic | magnetic properties aerogel chemical immobilization N-3-(trimethoxysilyl)propyl ethylenediamine single-ion magnet single-molecule magnet |
| url | https://www.mdpi.com/1420-3049/28/1/418 |
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