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

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.. Authors: Brekalo, Ivana [Ruđer Bošković Institute, Zagreb (Croatia); Georgetown Univ., Washington, DC (United States); McGill Univ., Montreal, QC (Canada)] (ORCID:0000000203095610); Lisac, Katarina [Ruđer Bošković Institute, Zagreb (Croatia)] (ORCID:0000000264975937); Ramirez, Joseph R. [Georgetown Univ., Washington, DC (United States)]; Pongrac, Petra [Ruđer Bošković Institute, Zagreb (Croatia); Univ. of Zagreb (Croatia)] (ORCID:0009000228676865); Puškarić, Andreas [Ruđer Bošković Institute, Zagreb (Croatia)] (ORCID:000000030726057X). DOE Contract: AC02-06CH11357. Subjects: additives; liquids; materials; mathematical methods; mixtures