Sustainable Synthesis of Diamondoid Ethers by High-Temperature Ball Milling

Alić Stolar, Jasna; Stolar, Tomislav; Štefanić, Zoran; Užarević, Krunoslav; Šekutor, Marina (2023) Sustainable Synthesis of Diamondoid Ethers by High-Temperature Ball Milling. ACS Sustainable Chemistry & Engineering, 11 (2). pp. 617-624. ISSN 2168-0485

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Abstract

Diamondoids have emerged as promising carbon-based nanomaterial building blocks because of their unique combination of exceptional properties and availability for selective functionalization. Until now, the chemical functionalization of diamondoids was primarily based on solution methods. However, the limited solubility of diamondoid derivatives and their tendency to sublimate at even slightly elevated temperatures made it difficult to prepare more extensive diamondoid derivatives. Here, we present the first mechanochemical synthesis of several diamondoid ethers differing in the type, size, and number of their hydrocarbon cage subunits. We found that the efficient preparation of these ethers is enabled solely by high-temperature ball milling conditions and does not proceed under ambient conditions. When compared to the conventional synthesis of the same ether derivatives, the calculated green chemistry metrics showed the enormous sustainability benefits of the mechanochemical synthesis. The mechanochemical approach includes shorter reaction times, a green inorganic base, a simplified workup procedure, comparable or superior reaction yields, and the elimination of solvents in the synthesis. Furthermore, crystal structures obtained from single-crystal X-ray diffraction (SCXRD) experiments confirmed the molecular structures of target products and gave insight into their intermolecular interactions in the solid state. From a perspective of the future applicability of these materials in nanotechnology, the cost and sustainability of their preparation are paramount. We demonstrated herein that mechanochemistry is a viable option for this challenge.

Item Type:	Article
Uncontrolled Keywords:	diamondoids; thermally controlled mechanochemistry; high-temperature ball milling; sustainable organic synthesis; ethers
Subjects:	NATURAL SCIENCES > Chemistry > Physical Chemistry NATURAL SCIENCES > Chemistry > Organic Chemistry
Divisions:	Division of Organic Chemistry and Biochemistry Division of Physical Chemistry
Projects:	Project title Project leader Project code Project type Diamantoidni sustavi s heteroatomima – priprava i primjena u razvoju naprednih materijala-DiamMat Marina Šekutor UIP-2017-05-9653 HRZZ Važnost mehanokemijske reaktivnosti u prebiotičkoj kemijskoj evoluciji i njezin prijenos na održivu kemijsku proizvodnju s niskim emisijama-PREBIOMECHEM Krunoslav Užarević IP-2020-02-4702 HRZZ
Depositing User:	Marina Šekutor
Date Deposited:	10 Jan 2025 09:01
URI:	http://fulir.irb.hr/id/eprint/9413
DOI:	10.1021/acssuschemeng.2c05283

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