Framework Isomerism in a Series of btb-Containing In-Derived Metal–Organic Frameworks

Abstract

The discovery of new inorganic building units for metal−organic framework (MOF) synthesis remains challenging. We hypothesized that incorporation of X-type halogen capping ligands on indium-building units would yield a series of previously unknown frameworks and the placement of the halogen could lead to framework isomerism. Herein we report the synthesis of three new MOFs; two (YCM-31 and YCM-32) contain an [In(CO 2 R) 3 Cl] − secondary building unit (SBU) and are framework isomers of each other. A third new MOF, ZJU-28′, contains an [In(CO 2 R) 4 ] − SBU and is a framework isomer of the known MOF ZJU-28. The conditions to control the syntheses of these isomers through ammonium-cation templation, along with the rationale for their formation are discussed.

Syntheses of ferrocene-functionalized indium-based metal–organic frameworks for third order nonlinear optical application

“…In addition, some high-valence metal centers (such as In 3+ ,Ti 4+ , Zr 4+ or Hf 4+ ), especially In 3+ , have been reported as efficient catalysts in multicomponent reactions, 19 and interestingly, they can also act as tetrahedral units (such as InN 2 (CO 2 ) 4 , InN 4 (CO 2 ) 4 , InN 4 (CO 2 ) 2 or In(CO 2 ) 4 ) by chelating coordination (two or more coordination atoms and forms a chelating ring with a central atom or ion) of organic ligands. [20][21][22][23][24][25][26][27][28] Some indium-based MOFs (In-MOFs) with 4-connected topologies can be reasonably designed and synthesized based on the In 3+ tetrahedral center with various ligands. [29][30][31][32][33] Considering the local and global charge balance, these frameworks are usually anionic and require cations as a guest, endowing them with ion exchange properties.…”

Molecular Intermediate in the Directed Formation of a Zeolitic Metal–Organic Framework

“…ZMOFs are a promising class of material that can combine advantageous properties of individual zeolitic or MOF structures (e.g., forbidden interpenetrations, large cavities, and aqueous stabilities). − Specifically, we describe the reaction pathway between Indium­(III) nitrate hydrate (In­(NO 3 ) 3 · x H 2 O) and 4,5-imidazoledicarboxylic acid (H 3 ImDC) that yields different ZMOFs in the presence of different SDAs (Scheme ). − The reaction between these two precursors highlights the importance of structure control: each of the MOFs shown in Scheme are constructed from the same metal and ligand, however different SDAs lead to different frameworks with different function, rho and med . − Similar directed conformational/framework isomerism is also observed in other indium-based metal–organic systems. − In this study, we focused on the SDA imidazole (HIm) that leads to an indium MOF with a sodalite ( sod ) topology (herein sod -InMOF, also known as sod -ZMOF). Our particular interest in ZMOFs, and particularly sod -InMOF with an anionic framework, stems from an inherent ability to control extra-framework cations and the resultant applications in gas separation and storage, − catalysis, , and beyond .…”

On the Role of Dioxane in the Synthesis of In-Derived MOFs

“…Our laboratory has used a 3/2 (v/v) DMF/dioxane solvent mixture for the synthesis of In-derived MOFs extensively due to high yields and the formation of higher quality crystalline materials compared to DMF-only systems. − To our knowledge the first reported use of dioxane as a cosolvent in the synthesis of In-derived MOFs was by Chen and Qian for the synthesis of ZJU-28 . While the use of dioxane in our hands routinely yielded materials with higher crystallinity, the origin of this effect was unknown and warranted further investigation.…”