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Tunable Fulleretic Sodalite MOFs: Highly Efficient and Controllable Entrapment of C60 Fullerene via Mechanochemistry

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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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
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”
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
Divisions: Division of Physical Chemistry
Project titleProject leaderProject codeProject type
Mehanokemijske i bezotopinske strategije za sintezu funkcionalnih poroznih materijala s naprednim fizičko-kemijskim i katalitičkim svojstvima-MECHADVANCEKrunoslav UžarevićPZS-2019-02-4129HRZZ
Studija važnosti spinskih međudjelovanja kao osnova za nove pristupe u istraživanju materijala-SPESMarina Ilakovac KvederIP-2018-01-3168HRZZ
Magneto-structural correlations in molecular magnetic complexes studied by electron spin resonance spectroscopy for financial supportDijana ŽilićUNSPECIFIEDDAAD-MZO
Depositing User: Krunoslav Užarević
Date Deposited: 18 Jan 2021 13:04
DOI: 10.1021/acs.chemmater.0c03796

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