Mechanochemical Solid Form Screening of Zeolitic Imidazolate Frameworks Using Structure-Directing Liquid Additives

Brekalo, Ivana; Lisac, Katarina; Ramirez, Joseph R.; Pongrac, Petra; Puškarić, Andreas; Valić, Srećko; Xu, Yizhi; Ferguson, Michael; Marrett, Joseph M.; Arhangelskis, Mihails; Friščić, Tomislav; Holman, K. Travis (2025) Mechanochemical Solid Form Screening of Zeolitic Imidazolate Frameworks Using Structure-Directing Liquid Additives. Journal of the American Chemical Society, 147 (31). pp. 27413-27430. ISSN 0002-7863

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Abstract

We demonstrate a systematic application of the mechanochemical liquid-assisted grinding (LAG) methodology to screen for forms of zinc imidazolate (ZnIm2), of fundamental importance as the simplest member of the zeolitic imidazolate framework materials family. The exploration of 45 different liquid additives, selected based on their molecular structure and physicochemical properties has resulted in eight different ZnIm2 topological forms, appearing in 13 crystallographically distinct solid forms (including two previously unknown forms of the crb (BCT) topology), amorphous phases, and the interrupted moc-Zn4Im8HIm. All prepared topological forms were also explored computationally, using dispersion-corrected periodic density functional theory (DFT) calculations, enabling the rationalization of screening outcomes, and setting the stage for future prediction of additive-directed metal–organic framework (MOF) synthesis. This first systematic exploration of LAG in screening for three-dimensional MOFs demonstrates the potential of the liquid additive to not only accelerate materials synthesis, but also to direct it toward topologically different MOFs. The discovery of novel forms of a material that already exhibits at least 21 crystallographically and functionally different forms provides a strong testimony on the power of mechanochemistry in metal–organic materials discovery.

Item Type:	Article
Uncontrolled Keywords:	mechanochemistry; templation; computational modelling
Subjects:	NATURAL SCIENCES > Chemistry
Divisions:	Division of Materials Chemistry Division of Physical Chemistry
Projects:	Project title Project leader Project code Project type Mehanokemijsko templatiranje potpomognuto računalnom kemijom za ciljanu i održivu sintezu funkcionalnih materijala Ivana Brekalo NPOO.C3.2.R2-I1.06.0049 EK
Depositing User:	Lorena Palameta
Date Deposited:	04 Sep 2025 08:29
URI:	http://fulir.irb.hr/id/eprint/9966
DOI:	10.1021/jacs.5c04043

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