Next Article in Journal
Reductive Deuteration of Acyl Chlorides for the Synthesis of α,α-Dideuterio Alcohols Using SmI2 and D2O
Next Article in Special Issue
First Example of Cage P4N4-Macrocycle Copper Complexes with Intracavity Location of Unusual Cu2I Fragments
Previous Article in Journal
Targeted Delivery of Sunitinib by MUC-1 Aptamer-Capped Magnetic Mesoporous Silica Nanoparticles
Previous Article in Special Issue
Transition Metal–(μ-Cl)–Aluminum Bonding in α-Olefin and Diene Chemistry
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 28
Issue 1
10.3390/molecules28010418
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica

by
Sergey Yu. Kottsov
1,
Maxim A. Shmelev
1,
Alexander E. Baranchikov
1,*,
Mikhail A. Kiskin
1,
Alim U. Sharipov
1,2,
Nikolay N. Efimov
1,
Irina K. Rubtsova
1,
Stanislav A. Nikolaevskii
1,
Gennady P. Kopitsa
3,4,
Tamara V. Khamova
4,
Ilya V. Roslyakov
1,5,
Igor L. Eremenko
1 and
Vladimir K. Ivanov
1,6
1
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 119991, Russia
2
Faculty of Technology of Inorganic Substances and High Temperature Materials, Mendeleev University of Chemical Technology of Russia, Moscow 125047, Russia
3
St.-Petersburg Nuclear Physics Institute, National Research Center “Kurchatov Institute”, Gatchina 188300, Russia
4
Grebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, St.-Petersburg 199034, Russia
5
Department of Materials Science, Lomonosov Moscow State University, Moscow 119991, Russia
6
Faculty of Chemistry, National Research University Higher School of Economics, Moscow 109028, Russia
*
Author to whom correspondence should be addressed.
Molecules 2023, 28(1), 418; https://doi.org/10.3390/molecules28010418
Submission received: 9 November 2022 / Revised: 15 December 2022 / Accepted: 27 December 2022 / Published: 3 January 2023
(This article belongs to the Special Issue Frontiers in Metal Complexes)
Browse Figures
Versions Notes

Abstract

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 m2·g−1, an apparent density of 0.403–0.740 cm3·g−1 and a porosity of 60–78%. The actual cobalt content in the aerogels was 0.01–1.50 mmol per 1 g of SiO2, 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)(NO3)2], 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 SiO2 resulted in a weakening of inter-ion interactions; the magnetization reversal energy barrier likewise increased from 4 to 18 K.
Keywords: magnetic properties; aerogel; chemical immobilization; N-3-(trimethoxysilyl)propyl ethylenediamine; single-ion magnet; single-molecule magnet; Raman spectroscopy; electron paramagnetic resonance magnetic properties; aerogel; chemical immobilization; N-3-(trimethoxysilyl)propyl ethylenediamine; single-ion magnet; single-molecule magnet; Raman spectroscopy; electron paramagnetic resonance

Share and Cite

MDPI and ACS Style

Kottsov, S.Y.; Shmelev, M.A.; Baranchikov, A.E.; Kiskin, M.A.; Sharipov, A.U.; Efimov, N.N.; Rubtsova, I.K.; Nikolaevskii, S.A.; Kopitsa, G.P.; Khamova, T.V.; et al. Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica. Molecules 2023, 28, 418. https://doi.org/10.3390/molecules28010418

AMA Style

Kottsov SY, Shmelev MA, Baranchikov AE, Kiskin MA, Sharipov AU, Efimov NN, Rubtsova IK, Nikolaevskii SA, Kopitsa GP, Khamova TV, et al. Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica. Molecules. 2023; 28(1):418. https://doi.org/10.3390/molecules28010418

Chicago/Turabian Style

Kottsov, Sergey Yu., 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, and et al. 2023. "Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica" Molecules 28, no. 1: 418. https://doi.org/10.3390/molecules28010418

APA Style

Kottsov, S. Y., Shmelev, M. A., Baranchikov, A. E., Kiskin, M. A., Sharipov, A. U., Efimov, N. N., Rubtsova, I. K., Nikolaevskii, S. A., Kopitsa, G. P., Khamova, T. V., Roslyakov, I. V., Eremenko, I. L., & Ivanov, V. K. (2023). Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica. Molecules, 28(1), 418. https://doi.org/10.3390/molecules28010418

Article Metrics

Back to TopTop