Stable Mg‑Metal–Organic Framework (MOF) and Unstable Zn-MOF Based on Nanosized Tris((4-carboxyl)phenylduryl)amine Ligand

By employment of a nanosized tris­[(4-carboxyl)-phenylduryl]­amine ligand (L) to assembly with the Zn²⁺ or Mg²⁺ ions, two non-interpenetrating microporous metal–organic frameworks (MOFs) constructed from chain-shaped building units are presented here. The Zn-MOF formulated as ((CH₃)₄N)­(Zn₄L₃)·28DMF (<b>FIR-4</b>; DMF = <i>N</i>,<i>N</i>-dimethylformamide, <b>FIR</b> denotes Fujian Institute of Research) is a nanoporous anionic framework, but it is unstable after the removal of guest molecules. In contrast, the Mg-MOF formulated as Mg₃L₂(H₂O)₂(DMA)₂·2.5DMA (<b>FIR-5</b>; DMA = <i>N</i>,<i>N</i>-dimethylacetamide) features a neutral framework with (3,8)-connected <b>tfz</b> topology derived from <b>kgd</b> subnets and has high permanent porosity with a Langmuir surface area of 1457 m²·g^–1

Cluster-Organic Framework Materials as Heterogeneous Catalysts for High Efficient Addition Reaction of Diethylzinc to Aromatic Aldehydes

To explore the catalytic activity of heterometallic cluster-organic frameworks, three 3d-3d heterometallic cluster-organic frameworks based on the cooperative assembly of tetrahedral Cu₄I₄ and metal-carboxylate clusters with potential open metal sites were synthesized and described in detail. The structure of <b>1</b> consists of tetrahedral [Cu₄I₄(INA)₄]^4– metalloligands (INA = isonicotinate) linking unusual Zn₈(μ₄-O)­(COO)₁₂(H₂O)₄ clusters into a (4,12)-connected network. Compound <b>2</b> features a 2-fold interpenetrating 4-connected <b>bbf</b>-type framework based on new [Cu₄I₄(INA)₂(DBO)₂]^2– metalloligands (DBO = 1,4-diazabicyclo[2.2.2]­octane) and paddle-wheel Zn₂(COO)₄ units. The 2-fold interpenetrating diamond-type framework <b>3</b> is constructed from tetrahedral [Cu₄I₄(INA)₄]^4– metalloligand and Mn₂(COO)₄(H₂O)₂(DMF) unit with potential open Mn centers. All three framework materials have notable catalytic activity on the diethylzinc addition to aromatic aldehydes, and the catalytic properties of compound <b>1</b> have been studied in detail. The results reveal that the heterogeneous catalysis of the diethylzinc addition to aromatic aldehydes by using cluster-organic framework as catalyst is determined by several experimental factors, such as temperature, reaction time, and the incorporation of electron-withdrawing groups in aromatic aldehydes

Tuning MOF Stability and Porosity via Adding Rigid Pillars

High stability and permanent porosity are the premise of general applicability for metal–organic framework materials (MOFs). By varying degrees of success on increasing the connectivity of the linear pillar 4,4′-bipyridine (bpy), two isostructural flexible frameworks [M₂(obb)₂(DMF)₂]·2DMF (<b>1</b>, M = Zn or Cu; H₂obb = 4,4′-oxybis­(benzoic acid), DMF = N,N-dimethylformamide) with no gas sorption are structurally modified into two rigid frameworks [Zn₂(obb)₂(bpy)]·DMF (<b>2</b>) and [Cu₂(obb)₂(bpy)_0.5(DMF)]·2DMF (<b>3</b>) with notable gas sorption and separation properties. Especially for <b>3</b>, it exhibits gas selective uptake for the adsorption of CO₂ over N₂ and CH₄ under 273 K and has an interesting physically lock effect in benzene and cyclohexane sorption. The results provide a successful strategy on tuning framework stability of flexible structures via adding rigid pillars

Stable Mg‑Metal–Organic Framework (MOF) and Unstable Zn-MOF Based on Nanosized Tris((4-carboxyl)phenylduryl)amine Ligand

By employment of a nanosized tris­[(4-carboxyl)-phenylduryl]­amine ligand (L) to assembly with the Zn²⁺ or Mg²⁺ ions, two non-interpenetrating microporous metal–organic frameworks (MOFs) constructed from chain-shaped building units are presented here. The Zn-MOF formulated as ((CH₃)₄N)­(Zn₄L₃)·28DMF (<b>FIR-4</b>; DMF = <i>N</i>,<i>N</i>-dimethylformamide, <b>FIR</b> denotes Fujian Institute of Research) is a nanoporous anionic framework, but it is unstable after the removal of guest molecules. In contrast, the Mg-MOF formulated as Mg₃L₂(H₂O)₂(DMA)₂·2.5DMA (<b>FIR-5</b>; DMA = <i>N</i>,<i>N</i>-dimethylacetamide) features a neutral framework with (3,8)-connected <b>tfz</b> topology derived from <b>kgd</b> subnets and has high permanent porosity with a Langmuir surface area of 1457 m²·g^–1

Microporous Metal–Organic Framework Based on Mixing Nanosized Tris((4-carboxyl)-phenylduryl)amine and 4,4′-Bipyridine Ligands for Gas Storage and Separation

The assembly of mixing nanosized tris­((4-carboxyl)­phenylduryl)­amine ligand and 4,4′-bipyridine ligand with Zn²⁺ ion leads to a new microporous framework <b>FIR-2</b> having pillared-layer structure and unusual (3,4,6)-connected topology, which exhibits large surface area and gas adsorption selectivity for the adsorption of CO₂ over N₂ or CH₄. The results reveal the potential application of the long tris­((4-carboxyl)­phenylduryl)­amine ligand on the construction of functional microporous metal–organic frameworks with interesting structural topologies for gas storage and separation

Gas Sorption, Second-Order Nonlinear Optics, and Luminescence Properties of a Series of Lanthanide–Organic Frameworks Based on Nanosized Tris((4-carboxyl)phenylduryl)amine Ligand

By controlling the pH value of the reaction system, two sets of lanthanide (Ln)–tris­((4-carboxyl)­phenylduryl)­amine (Ln = Ce, Pr, Nd, Sm) frameworks have been generated. Four isostructural noninterpenetrating frameworks (<b>FIR-8</b> to <b>FIR-11</b>) are constructed from rod-shaped secondary building units and four other isostructural frameworks (<b>FIR-12</b> to <b>FIR-15</b>) based on single Ln nodes are described as 8-fold interpenetrating dia-type nets. Gas sorption measurements for <b>FIR-8</b> give a Langmuir surface area of 633.8 m²·g^–1 and a H₂ uptake of 165.2 cm³·g^–1 at 77 K and 1 atm. However, <b>FIR-12</b> with smaller pores can hardly adsorb any N₂ and H₂. Because both <b>FIR-8</b> and <b>FIR-12</b> crystallize in acentric space group, the second-harmonic generation (SHG) measurements indicate that both of them display strong powder SHG efficiencies, which are approximately 8 and 3 times as strong as that of a potassium dihydrogen phosphate powder. In addition, the fluorescent emissions of all compounds in the solid state are also investigated in detail

Comparative Study of Activation Methods on Tuning Gas Sorption Properties of a Metal–Organic Framework with Nanosized Ligands

Presented here is a new porous metal–organic framework based on a nanosized tris­((4-carboxyl)­phenylduryl)­amine ligand, which features a 2-fold interpenetrating <b>hms</b> network and shows distinct gas adsorption behaviors dependent on different activation methods

Organic Cation Templated Synthesis of Three Zinc–2,5-Thiophenedicarboxylate Frameworks for Selective Gas Sorption

Three anionic Zn­(II)–organic frameworks with 2,5-thiophenedicarboxylate ligand have been synthesized solvothermally. They exhibit different 3D net topologies but all contain trinuclear [Zn₃(COO)₈] building units. Compound <b>1</b> shows an 8-connected <b>bcg</b> net just based on [Zn₃(COO)₈] nodes, while compound <b>2</b> displays an 8-connected <b>bcu</b> net based on two similar [Zn₃(COO)₈] nodes. Interestingly, compound <b>3</b> represents a novel (4,8)-connected <b>flu</b> net based on the trinuclear nodes [Zn₃(COO)₈] and the binuclear nodes [Zn₂(COO)₄]. Gas sorption measurements indicate that the desolvated host <b>1-ht</b> exhibits permanent porosity with Langmuir surface area of 630.5 m²·g^–1 and a H₂ uptake of 109.5 cm³·g^–1 at 77 K and 1 atm, as well as a selective sorption of CO₂ over N₂ at 0 °C and ambient pressure

Gas Sorption, Second-Order Nonlinear Optics, and Luminescence Properties of a Series of Lanthanide–Organic Frameworks Based on Nanosized Tris((4-carboxyl)phenylduryl)amine Ligand

By controlling the pH value of the reaction system, two sets of lanthanide (Ln)–tris­((4-carboxyl)­phenylduryl)­amine (Ln = Ce, Pr, Nd, Sm) frameworks have been generated. Four isostructural noninterpenetrating frameworks (<b>FIR-8</b> to <b>FIR-11</b>) are constructed from rod-shaped secondary building units and four other isostructural frameworks (<b>FIR-12</b> to <b>FIR-15</b>) based on single Ln nodes are described as 8-fold interpenetrating dia-type nets. Gas sorption measurements for <b>FIR-8</b> give a Langmuir surface area of 633.8 m²·g^–1 and a H₂ uptake of 165.2 cm³·g^–1 at 77 K and 1 atm. However, <b>FIR-12</b> with smaller pores can hardly adsorb any N₂ and H₂. Because both <b>FIR-8</b> and <b>FIR-12</b> crystallize in acentric space group, the second-harmonic generation (SHG) measurements indicate that both of them display strong powder SHG efficiencies, which are approximately 8 and 3 times as strong as that of a potassium dihydrogen phosphate powder. In addition, the fluorescent emissions of all compounds in the solid state are also investigated in detail

Gas Sorption, Second-Order Nonlinear Optics, and Luminescence Properties of a Multifunctional srs-Type Metal–Organic Framework Built by Tris(4-carboxylphenylduryl)amine

A chiral 8-fold interpenetrating srs-type metal–organic framework <b>FIR-28</b> (FIR denotes Fujian Institute of Research) exhibits a surface area of 1029 m²/g and high C₃H₈/CH₄ separation capacity in excess of 154 and displays strong powder second-harmonic-generation efficiency, with more than half over potassium dihydrogen phosphate powder. Moreover, the luminescence properties of <b>FIR-28</b> are dependent on the solvent guests