Martinez, Valentina; Karadeniz, Bahar; Biliškov, Nikola; Lončarić, Ivor; Muratović, Senada; Žilić, Dijana; Avdoshenko, Stanislav M.; Roslova, Maria; Popov, Alexey A.; Užarević, Krunoslav (2020) Tunable Fulleretic Sodalite MOFs: Highly Efficient and Controllable Entrapment of C60 Fullerene via Mechanochemistry. Chemistry of Materials, 32 (24). pp. 10628-10640. ISSN 0897-4756
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Abstract
Encapsulation and confinement of fullerene guests in metal-organic frameworks (MOFs) lead to a novel class of crystalline fulleretic materials with unique physicochemical properties and a broad field of potential applications. The control over the amount of target guests confined in the MOF structure remains a significant challenge, which is particularly pronounced in the confinement of hardly accessible fullerene derivatives. The main strategies used in constructing fulleretic composites are limited by the solubility of components used and solvent versus guest competition for inhabitation of the framework voids. As mechanochemical procedures often overcome these issues, we developed here solvent-free processing by ball milling to gain control over the encapsulation of bulky and rigid C60-fullerene into a sodalite MOF with large cages and narrow cage-apertures. A rapid, green, efficient, and stoichiometry-controlled mechanochemical processing afforded four model C60@zeolitic-imidazolate framework 8 (ZIF-8) crystalline materials containing target 15, 30, 60, and 100 mol % of fullerene entrapped in the accessible cages of the model sodalite zeolitic-imidazolate framework 8 (ZIF-8), in stark contrast to the solution-based strategies that resulted in almost no loading. Varying the fullerene content affects the framework’s vibrational properties, color and luminescence of the composites, and the electron-dose radiation stability. The computational and spectroscopic studies show that the fullerene is accommodated in the cage’s center and that the cage-to-cage transport is a hardly feasible and energetically unfavored process. However, the fast release of C60 molecules from ZIF-8 can be effectively controlled by the pH. The entrapment of fullerene molecules in ZIF-8 resulted in their effective isolation even in higher loadings, paving the way to other tunable porous fulleretics containing single-molecule magnets or nanoprobes available on low scales.
| Item Type: | Article | ||||||||||||||||
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| Additional Information: | “This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.chemmater.0c03796” | ||||||||||||||||
| Uncontrolled Keywords: | Mechanochemistry; Carbon nanomaterials; Nanospheres; Metal organic frameworks; Encapsulation; Aromatic compounds; ZIF-8; Hybrid MOFs | ||||||||||||||||
| Subjects: | NATURAL SCIENCES > Chemistry > Physical Chemistry NATURAL SCIENCES > Chemistry > Inorganic Chemistry NATURAL SCIENCES > Chemistry > Applied Chemistry |
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| Divisions: | Division of Physical Chemistry | ||||||||||||||||
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| Depositing User: | Krunoslav Užarević | ||||||||||||||||
| Date Deposited: | 18 Jan 2021 13:04 | ||||||||||||||||
| URI: | http://fulir.irb.hr/id/eprint/6148 | ||||||||||||||||
| DOI: | 10.1021/acs.chemmater.0c03796 |
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