Using geometric simulation software 'GASP' to model conformational flexibility in a family of zinc metal–organic frameworks. (28th April 2021)

• Record Type: Journal Article
• Authors: Gee, William J.; Wells, Stephen A.; Teat, Simon J.; Raithby, Paul R.; Burrows, Andrew D.
• Is Part Of: New journal of chemistry. Volume 45:Number 19(2021)
• Page Start: 8728
• Page End: 8737
• Publication Date: 2021-04-28
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/d1nj01158h
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : Synthesis with different solvents leads the same metals and ligands to assemble into geometrically and topologically distinct frameworks, aided by intrinsic flexibility of the ligand. Abstract : Here, a new tripodal tricarboxylic acid ligand, 4, 4′-(4′-(4′-carboxy-[1, 1′-biphenyl]-4-yl)-[2, 2′:6′, 2′′-terpyridine]-5, 5′′-diyl)-dibenzoic acid (H3 cbt ), was synthesised using a three-step convergent strategy. Subsequent reactions with zinc(ii ) nitrate hexahydrate yielded three metal–organic frameworks (MOFs). The three MOFs, [Zn(Hcbt )]·4DMF (1 ), [Zn(Hcbt )]·4DMSO·1.5H2 O·DMF (2 ), and [Zn(Hcbt )]·2DMF·3H2 O (3 ), each adopt flexible interdigitated 2D net topologies. Framework 1 has DMF-filled channels that retain porosity upon desolvation, with a measured BET surface area of 248 m 2 g −1 . Framework 2 possesses larger DMSO-containing channels that collapse upon desolvation, resulting in near-equivalent porosity values to framework 1 . In silico calculations and topological considerations determined using the geometric simulation software GASP dictate that framework 2 can feasibly alter conformation to approximate 1, but cannot perfectly replicate the interdigitated motif. Framework 3 formed when wet solvents were used to synthesise 1 . Interestingly, the interdigitated structure of 3 contains a unique carboxylate binding mode that precludes its subsequent adoption by either 1 or 2 upon their exposure to water. This diverse array of structural considerations recommends this MOF family for modelling using GASP. Interrogating frameworks 1–3 using this software provided insights that justified experimentally observed conformational trends, as well as barriers to interconversion between members of this MOF family. In a broader sense, this work demonstrates the wider applicability of GASP software to modelling structural changes within flexible MOF materials.