Two topologically different 3D Cu^II metal–organic frameworks assembled from the same ligands: control of reaction conditions

Abstract

Bifunctional ligands containing both carboxylic and sulfonate groups can adopt versatile coordination modes to produce novel metal–organic frameworks (MOFs) with high‐dimensional networks and interesting topologies. Using 2,2′‐disulfonylbiphenyl‐4,4′‐dicarboxylic acid (H4L) as a linker and 4,4′‐bipyridine (4,4′‐bpy) as a co‐ligand, two novel 3D CuII MOFs, {[Cu2(L)(4,4′‐bpy)2.5(H2O)]·1.7H2O}n, (1), and {[Cu2(L)(4,4′‐bpy)2]·DMA·3H2O}n, (2), have been synthesized and structurally characterized by X‐ray crystallography (DMA is N,N‐dimethylacetamide). MOF (1) shows an unprecedented trinodal 4,4,5‐connected topology network with the Schläfli symbol (4.62.73)(43.65.7.8)(6.73.8.10), while MOF (2) indicates a binodal 4,6‐connected fsc network with the Schläfli symbol (44.610.8)(44.62). MOFs (1) and (2) were further characterized by elemental analysis, IR spectroscopy, powder X‐ray diffraction and thermogravimetric analysis. MOF (1) shows a high water and chemical stability. The proton conductivity of (1) and CO2 adsorption of (2) were also investigated.

Coordination Polymers Driven by Carboxy Functionalized Picolinate Linkers: Hydrothermal Assembly, Structural Multiplicity, and Catalytic Features

“…As a result, a dinodal 4,4-linked net with a (4 2 .6.8 3 ) point symbol and a unique topology is generated (Figure c). This compound can also be considered as a rod-like structure and contributes to an important family of MOFs with unique or rare types of topologies. − Further simplification of the framework using ToposPro software and considering the {Cd 2 (μ-COO) 2 } motifs as the 6-connected nodes results in a binodal 3,6-linked net with a jxj topology and a point symbol of (4 2 .6) 2 (4 4 .6 2 .8 9 ). , …”

Porosity regulation of metal–organic frameworks for high proton conductivity by rational ligand design: mono- versus disulfonyl-4,4′-biphenyldicarboxylic acid

“…4-Iodo-3-sulfobenzoic acid was synthesized according to the reference protocols. 33,34 1 H NMR spectra were recorded on a Bruker AM 400 MHz spectrometer in DMSO- d 6 solution, and the chemical shifts are in ppm. FT-IR spectra were recorded on a Nicolet 380 FT-IR instrument (KBr pellets).…”

“…19,26 Commonly used ligands for the preparation of proton conductive MOFs include dipotassium-3,3′-disulfonyl-4,4′-biphenyldicarboxylic acid (3,3′- DSBPDC ), 27 3,3′-disulfonyl-benzophenone-4,4′-dicarboxylic acid ( DSBODC ), 28 3,3′-disulfonyl-diphenylsulfone-4,4′-dicarboxylic acid ( DSDPSDC ), 29 disodium 2,2′-disulfonate-4,4′-oxydibenzoic acid ( DSOA ), 30–32 and 2,2′-disulfonyl-4,4′-biphenyldicarboxylic acid (2,2′- DSBPDC ). 33,34 All these ligands have two sulfonyl groups, which can be easily deprotonated to bind metal centers due to the stronger chelating ability of –SO 3 − groups to form cyclic coordinated configurations with neighboring –CO 2 − or –SO 3 − groups (Scheme 1). 19,35 The coordination of the –SO 3 − group to metal centers will reduce the proton concentration and the porosity of the resulting MOFs, so that the proton conductivity may be greatly decreased.…”

pH-Induced Two Co (II) Metal–Organic Frameworks with Different Topologies: Magnetism and CO2/CH4 Separation

“…Zhu et al has designed and assembled two 3D Cu II MOFs under different solvothermal conditions by tuning the reaction temperature, time, and solvent. 27 Sarkar and co-workers synthesized two MOFs by changing the metal centers, Zn-MOF has good catalytic properties, while Co-MOF has antiferromagnetic properties, which is due to the difference in the coordination environment of the metal center of the two MOFs, resulting in their different structures and properties. 28 Therefore, regulating the structure of MOFs by changing the conditions of the self-assembly process of MOFs remains a great challenge in the field of crystal engineering.…”

“…On the other hand, the different synthesis conditions of MOFs will lead to different topologies of MOFs, further changing the performance of MOFs. Zhu et al has designed and assembled two 3D Cu II MOFs under different solvothermal conditions by tuning the reaction temperature, time, and solvent . Sarkar and co-workers synthesized two MOFs by changing the metal centers, Zn-MOF has good catalytic properties, while Co-MOF has antiferromagnetic properties, which is due to the difference in the coordination environment of the metal center of the two MOFs, resulting in their different structures and properties .…”