Threefold Interpenetration Research Articles

Carboxamide functionality grafted entangled Co(II) framework as a unique hydrogen-bond-donor catalyst in solvent-free tandem deacetalization-Knoevenagel condensation with pore-fitting-mediated size-selectivity.

Concerning environmentally benign catalysis with reduced chemical usage, less energy consumption, and waste minimization, metal-organic frameworks (MOFs) with spatially isolated task-specific functionalities not only execute atom-economic important reactions but also enable size-exclusive catalysis at the interface of structure-function synergy. Herein, we synthesized a bipillar-layer Co(II) MOF from the dicarboxylate ligand and carboxamide moiety grafted pyridyl linker. The framework contains a [Co2(COO)4N4] secondary building unit (SBU) and shows excellent hydrolytic stability due to ample non-covalent interactions among the highly conjugated aromatic struts. Notably, the carboxamide functionalities remain free and are perfectly positioned throughout the one-dimensional channels of the framework, wherein three-fold interpenetration of the structure largely increases their density along the pore wall. Benefiting from these structural features, the activated MOF acts as an unprecedented organocatalyst in tandem deacetalization-Knoevenagel condensation towards electronically assorted substrates that were additionally characterized using single-crystal X-ray diffraction. Importantly, the reaction occurs under solvent-free mild conditions, and high catalyst reusability is recorded. In this one-pot cascade reaction, substrates with molecular dimensions larger than that of the three-fold interpenetration generated optimized pore-aperture undergo insignificant conversion, and therefore a rare molecular-dimension-induced size-selectivity is demonstrated. The catalytic route is detailed based on a battery of control experiments, including juxtaposing the performance of an isostructural MOF without any linker functionalization. Compared to the common Lewis acid mediated route, the results explicitly corroborate the first-ever substrate activation via hydrogen bonding to prepare coumarin derivatives via a tandem pathway, and shed light on this futuristic unconventional catalysis using contemporary materials and avoiding major operative glitches.

Designing Multicomponent Metal–Organic Frameworks with Hierarchical Structure-Mimicking Distribution for High CO2 Capture Performance

By utilizing a mixed-ligand strategy, a novel multicomponent Cu-metal-organic framework (MOF) (JLU-MOF107) has been successfully synthesized. JLU-MOF107 has an unusual hierarchical structure-mimicking distribution structure. The triangular 4,4',4″-benzene-1,3,5-triyl-tribenzoate (BTB) ligand and the binuclear Cu cluster form a threefold interpenetration layer, while the linear ligand 1,4-phenylene-4,4'-bis(1,2,4-triazole) (p-tr2ph) and tetranuclear Cu cluster form a noninterpenetration pillared-layer structure. Then, the two types of layers are connected by tetranuclear Cu clusters to construct the final sandwichlike framework. JLU-MOF107 exhibits good water and humidity stability. Due to the presence of various active sites and pores, JLU-MOF107 shows an outstanding performance for CO2 capture (171.0 cm3 g-1 at 273 K). Density functional theory (DFT)-based calculations further prove the interactions between CO2 molecules and multiple active sites. The innovative synthesis of this multicomponent structure offers a new perspective on making hierarchical porous materials and multifunctional MOFs.

A novel three-fold interpenetration 3D Cd-based coordination polymer for the sensing of glutamate in aqueous medium and calf serum

As a special biomarker for many nervous system diseases, Glutamate (Glu) plays an important role in clinical application. Therefore, it is of great significance to sense Glu sensitively in aqueous medium or serum. Here, a novel three-fold interpenetration 3D framework of {[Cd (HTCPB) (4,4′-bbib)]·2H2O}n (1) (H3TCPB ​= ​1,3,5-tris(4-carbonylphenyloxy)benzene, 4,4′-bbib ​= ​4,4′-bis(benzoimidazo-1-yl)biphenyl) (1) has been successfully synthesized and characterized by single-crystal X-Ray diffraction (SCXRD), X-ray powder diffraction analyses (PXRD), thermogravimetric (TG) and X-ray photoelectron spectroscopy (XPS). Stability experiments show that 1 has excellent water and thermal stability. And luminescence experiments demonstrated that 1 can selectively and sensitively sense Glu in aqueous solution with the limit of detection (LOD) being 1.15 ​× ​10-7 ​M. Meanwhile, the detection concentration of 1 towards Glu in serum is 4.31 ​× ​10-5 ​M, which is far lower than that of Glu (4 ​× ​10-4 ​M) in the blood of patients with glioma. In addition, the interaction between carboxylate groups (-COOH) of H3TCPB ligands in 1 and amino-groups (−NH2) of Glu is mainly responsible for the turn-on phenomenon of 1. These results provide a platform of 1 for sensing Glu in clinical application.

Template effect of innocent and coordinating anions on the formation of interpenetrated 2D and 3D networks: methyl orange and iodine sorption studies

A pyridyl based Schiff base resulted in a 2D staircase network (CP1) with Cd(ii) when ClO4− is the counter anion while the use of benzene-1,3-disulphonate counter anion resulted in a novel 3D Cd(ii) coordination polymer with threefold interpenetration (CP2).

Synthesis and Characterization of 2D and 3D Zinc(II) Coordination Polymers with High Photocatalytic Activities for Removal of Methylene Blue Dye

Two zinc(II) coordination polymers (CPs) {[Zn2(L)(MIPA)2]·2H2O}n (1) and {[Zn(L)(H2FA)]·2H2O}n (2) were synthesized via hydrothermal reaction by employment the 5‐methylisophthalic acid (H2MIPA) or 4,4‐(hexafluoroisopropylidene)diphthalic acid (H4FA) and the flexible ligand 1,6‐bis(2‐methylbenzimidazol‐1‐yl)hexane (L). The CPs were characterized by physicochemical and spectroscopic methods as well as by single‐crystal X‐ray diffraction analysis. CP 1 possesses a rare 3D threefold interpenetration framework with coe topology, CP 2 displays a 2D corrugated network with a sql network with point symbol of (44·62). Both CPs exhibited high activities for the photocatalytic degradation of methylene blue in water. The photocatalytic mechanism was also investigated.

Encapsulation of Silver Nanoparticles in an Amine-Functionalized Porphyrin Metal-Organic Framework and Its Use as a Heterogeneous Catalyst for CO2 Fixation under Atmospheric Pressure.

A new porphyrin-based compound, [Zn3 (C40 H24 N8 )(C20 H8 N2 O4 )2 (DEF)2 ](DEF)3 (1; DEF=N,N-diethylformamide), has been synthesized by employing 5,10,15,20-tetrakis(4-pyridyl)porphyrin, 1,2-diamino-3,6-bis(4-carboxyphenyl)benzene, and Zn2+ salt at 100 °C under solvothermal conditions. The structure, as determined by single-crystal XRD studies, is three-dimensional with threefold interpenetration. The usefulness of free -NH2 groups in the ligand was exploited for anchoring silver nanoparticles through a simple solution-based route. The silver-loaded sample, Ag@1, was characterized by powder XRD, energy-dispersive X-ray spectroscopy, high-resolution TEM, SEM, X-ray photoelectron spectroscopy, and inductively coupled plasma MS analysis, which clearly indicated that silver nanoparticles with a size of 3.83 nm were uniformly distributed within the metal-organic framework (MOF). The Ag@1 sample was evaluated for possible catalytic activity for the carboxylation of a terminal alkyne by employing CO2 under atmospheric pressure; this gave excellent results. The Ag@1 catalyst was found to be robust, active, and recyclable. The present studies suggest that porphyrin MOFs not only exhibit interesting structures, but also show good heterogeneous catalytic activity towards the fixation of CO2 .

Series of Mn(II)/Mg(II)/Zn(II) Coordination Polymers with Azo/Alkene Functionalized Ligands

A series of six novel coordination polymers based on Mn(II)/Mg(II)/Zn(II) metal ions with azo/alkene functionalized carboxylic acid have been synthesized and well-characterized using several state-of-art techniques. Compound 1, {[Mn2(ABDCA)2(DPE)(DMF)2]·2DMF}n, (where ABDCA = Azobenzene-4,4′-dicarboxylic acid, DPE = 1,2-Di(4-pyridyl)ethylene, and DMF = N,N′-Dimethylformamide) is a three-dimensional structure with threefold interpenetration. Compound 2, {[Mn3(ABDCA)3(DMF)4]·2DMF}n contains Mn3O16 cluster unit which is connected with ABDCA ligands to form a two-dimensional layered structure. Compound 3, {[Mg3(ABDCA)3(DMF)4]·4DMF}n contains Mg3O16 clusters, associated with ABDCA ligands, forming the 3D structure. Coordination polymers 4 and 5 ({[Zn(ABDCA)(2,2′-BPy)]·H2O}n, (4), {[Zn(SDCA)(2,2′-BPy]}n, (5)), respectively, (where SDCA = stilbene-4,4′-dicarboxylic acid and 2,2′-BPy = 2,2′-Bipyridine) are identical structures with a difference in carboxylate ligand. In both cases, the one-dimensional chains are ...

A three-dimensional supramolecular framework based on the interlinkage of an interpenetrating diamondoid coordination network

In the development of coordination-driven crystalline materials, O- and N-atom donors from carboxylate and pyridyl-based ligands are widely used classes of multidentate bridging ligands composed of several terminal coordinating groups linked by either rigid or flexible spacers. The rigidity of the ligands can play a vital role in the determination of the structures formed. A new CdII supramolecular compound, namely poly[μ-adipato-κ2O1:O4-μ-adipato-κ4O1,O1':O4,O4'-diaquabis[μ-1,4-bis(pyridin-4-yl)-1,3-butadiene-κ2N:N']dicadmium(II)], [Cd2(C6H8O4)2(C14H12N2)2(H2O)2]n, (I), has been synthesized by the self-assembly of Cd(NO3)2·4H2O, adipic acid (hexane-1,6-dioic acid; H2adp) and the dipyridyl ligand 1,4-bis(pyridin-4-yl)buta-1,3-diene (1,4-bpbd) under hydrothermal conditions. Single-crystal X-ray diffraction analysis reveals that each CdII centre is located in a distorted octahedral coordination environment, coordinated by one water O atom, three carboxylate O atoms from two different adp2- ligands and two N atoms from two different 1,4-bpbd ligands. The Cd(H2O) units are interconnected by the μ2,κ2-adp2-, μ2,κ4-adp2- and 1,4-bpbd ligands, which lie across centres of inversion, to give a 66-dia network. Large cavities within a single diamondoid network permit the mutual threefold interpenetration of crystallographically equivalent frameworks. Hydrogen-bonding interactions between the coordinated water molecules and adp2- carboxylate O atoms anchor the interpenetrating networks into a unique three-dimensional supramolecular structure. Topologically, taking the coordinated water molecules and CdII centres as nodes, the whole architecture can be simplified as a binodal (3,7)-connected supramolecular framework. The identity of (I) was further characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis and powder X-ray diffraction. The solid-state photoluminescence properties of (I) were also investigated.

Construction and properties investigation of propeller type and three-fold interpenetration topology Mn(II) complexes

Two new complexes, namely [(Iptp)4(MnCl2)5·6DMF] (1) and [(Iptp)2(tpa)3·4DMF]n (2) have been synthesized by solvothermal method based on terpyridine ligand: 4′-(4-(1H-imidazol-1-yl)phenyl)-2,2′:6′,2″-terpyridine (Iptp) and auxiliary ligand p-phthalic acid (H2tpa), respectively. Single crystal X-ray diffraction analyses reveal that complex 1 is a propeller type pentanuclear zero dimensional structure. While complex 2 is a three-dimensional structure, and has a topological structure of three-fold interpenetrating networks. Thermogravimetric analysis indicate 1 and 2 have good thermal stability. Furthermore, solid fluorescence spectra properties of two complexes were also investigated, and the result shows the fluorescence intensity both of complex 1 and complex 2 are weaker than that of the Iptp ligand.

Heterogeneous catalysis with a coordination modulation synthesized MOF: morphology-dependent catalytic activity

We report control over morphology of a micro-porous three-fold interpenetration amide-functionalized Zn(ii)-based MOF, [Zn2(oba)2(bpta)]·(DMF)3, TMU-22, for Knoevenagel condensation through coordination modulation growth.

Formation of a Polythreaded, Metal–Organic Framework Utilizing an Interlocked Hexadentate, Carboxylate Linker

A unique hexacarboxylate linker was prepared on the basis of an interlocked [2]rotaxane motif. The linker contains four carboxylate groups attached to a rigid, H‐shaped axle and two carboxylate units appended to a crown ether wheel. The resulting ZnII‐based metal–organic framework material has a unique lattice, in which three independent 3‐periodic frameworks (threefold interpenetration) are interconnected only by virtue of the threading of their individual components in the rotaxane linker.

Sodium‐Ion Batteries: High Power–High Energy Sodium Battery Based on Threefold Interpenetrating Network (Adv. Mater. 12/2016)

Sodium‐Ion Batteries: High Power–High Energy Sodium Battery Based on Threefold Interpenetrating Network (Adv. Mater. 12/2016)

High Power–High Energy Sodium Battery Based on Threefold Interpenetrating Network

A 3D tricontinuous Na3 V2 (PO4 )3 :reduced graphene oxide-carbon nanotube cathode is directly deposited on the current collector without any conductive additives or binders by a facile electrostatic spray deposition (ESD) technique. Such an electrode displays excellent rate capability and long cycling stability, which is rather typical of supercapacitors but is connected here with the much higher energy density of an efficient battery electrode.

Synthesis and characterization of copper(II) and nickel(II) coordination polymers containing 2,6-naphthalenedicarboxylate and bis(benzimidazole) ligands

Two coordination polymers, namely [Ni(L1)-(ndc)(H2O)] n (1) and [Cu(L2)0.5(ndc)] n (2) (L1 = 1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, L2 = 1,4-bis(2-methylbenzimidazole)butane, H2ndc = 2,6-naphthalenedicarboxylic acid) have been synthesized and characterized by single-crystal and powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and elemental analysis. Complex 1 features a 2D 3-connected hcb network with 63 topology, which is further extended into a 3D supramolecular framework by O–H···O hydrogen bonding interactions. Complex 2 possesses a 3D threefold interpenetrating (4,5)-connected xah topological network, and its Schlafli symbol is (42.62.82)(46.64). Both complexes exhibit intense luminescence emissions in the solid state and promising catalytic activities for the degradation of Congo red azo dye in a Fenton-like process.

A series of coordination polymers based on a V-shaped multicarboxylate and bisimidazole ligands: Synthesis, characterization and luminescent properties

Based on a V-shaped multicarboxylic acid and various bisimidazole ligands, six new coordination polymers, namely, [Zn4(otba) (1,4-bix)4]·3H2O (1), [Ni4(otba)2(1,4-bix)3(H2O)2]·2H2O (2), [Zn2(H2otba)2(bib) (H2O)2] (3), [Cd2(H2otba)2(bib)]·2H2O (4), [Zn3(otba)2(bidpe)2(H2O)2] (5), [Ni2(H2otba)2(bidpe)3(H2O)2]·H2O (6) (H4otba = 3,5,3′,5′-oxytetrabenzoic acid, 1,4-bix = 1,2-bis(imidazol-1-ylmethyl)benzene, bib = 1,4-bis(imidazol-1-yl)benzene and bidpe = 4,4’-bis(imidazol-1-yl)diphenyl ether) have been hydrothermally synthesized and structurally characterized. Compound 1 displays an uncommon hexanodal 3D 4-connected network. Compound 2 features a trinodal 3D (4, 4, 6)-connected framework. Compound 3 shows an interesting polythreaded 1D→3D species. Compound 4 exhibits a binodal 3D (3, 8)-connected network. Compound 5 displays a three-fold interpenetration of trinodal (3, 3, 4)-connected network. Compound 6 shows a five-fold interpenetration of five-connected bilayer network. The luminescent properties of compounds 1, 3, 4 and 5 were also measured.

Syntheses, Structures, and Luminescent Properties of d10 Coordination Polymers with 2‐(4‐Carboxyphenyl)‐imidazo[4, 5‐f]‐1, 10‐phenanthroline and 1, 3‐Benzenedicarboxylate Derivatives

AbstractFour ZnII/CdII coordination polymers (CPs) based on 2‐(4‐carboxy‐phenyl)imidazo[4, 5‐f]‐1, 10‐phenanthroline (HNCP) and different derivatives of 5‐R‐1, 3‐benzenedicarboxylate (5‐R‐1, 3‐BDC) (R = NO2, H, OH), [Zn(HNCP)(5‐NO2‐1, 3‐BDC)]n (1), [Cd(HNCP)(5‐NO2‐1, 3‐BDC)]n (2), [Zn(HNCP)(1, 3‐BDC)(H2O)2]n (3), and {[Zn(HNCP)(5‐OH‐1, 3‐BDC)(H2O)·H2O}n (4) were synthesized under hydrothermal conditions. Compounds 1–4 were determined by elemental analyses, IR spectroscopy, and single‐crystal and powder X‐ray diffraction. Compounds 1 and 2 are isomorphous, presenting a 4‐connected uninodal (4, 4)‐sql 2D framework with threefold interpenetration, which are further extended into the three‐dimensional (3D) supramolecular architecture through π···π stacking interactions between the aryl rings of 5‐NO2‐1, 3‐BDC. Compared to compound 1, 3 is obtained by using different reaction temperatures and metal‐ligand ratios, generating a 3D framework with –ABAB– fashion via π···π stacking interactions. Compound 4 is a 1D chain, which is further extended into a 3D supramolecular net by hydrogen bonds and π···π stacking interactions. The thermogravimetric and fluorescence properties of 1–4 were also explored.

混合配体构筑的Zn(II)金属有机骨架化合物的合成、 结构与荧光性质

在水热条件下, 利用锌离子与2种有机配体合成出1个结构新颖的金属有机骨架化合物[Zn 2 (BPDC)(IN) 2 ] (H 2 BPDC=4,4'-联苯二羧酸; HIN=异烟酸), 并通过单晶X射线衍射、红外光谱、热重分析和荧光光谱等对该化合物进行了表征. 结果表明, 该化合物结构中Zn离子与BPDC的羧基形成双核金属次级结构单元[Zn 2 (-CO 2 ) 2 (IN) 2 ], 相邻次级结构单元通过IN配离子连接形成[Zn 2 (-CO 2 ) 2 (IN) 2 ] ∞ 二维层面, 相邻的二维层通过BPDC相互连接形成具有三重互穿的简单格子拓扑结构. 该化合物表现出良好的荧光性质.

Synthesis, structure and luminescence properties of two new acylamide metal-organic frameworks showing 4-connected CdSO₄ and a threefold interpenetrating dia net.

Two new acylamide metal-organic frameworks (MOFs), based on mixed N- and O-donor ligands, with 4-connected topologies have been obtained, namely poly[[μ2-N(1),N(4)-bis(pyridin-3-yl)terephthalamide]bis(μ3-4,4'-oxydibenzoato)dizinc(II)], [Zn2(C14H8O5)2(C18H14N4O2)]n, (1), and poly[[(μ2-benzene-1,4-dicarboxylato)[μ2-N(4),N(4')-bis(pyridin-3-yl)-[1,1'-biphenyl]-4,4'-dicarboxamide]dicadmium(II)] dihydrate], {[Cd(C8H4O4)(C24H18N4O2)]·2H2O}n, (2). Complex (1) is a 4-connected CdSO4 net with no interpenetration, where the Zn(II) cation is regarded as a 4-connecting node with square geometry. Complex (2) is a 4-connected dia net with threefold interpenetration, where the Cd(II) cation acts as a 4-connecting node with tetrahedral geometry. The results of thermogravimetric and luminescence analyses are described in detail.

Co‐MOFs Containing Flexible α,ω‐Alkane‐dicarboxylates and Bis(imidazole) Ligands: Synthesis, Structure, and Properties

AbstractThree structurally related flexible bis(imidazole) ligands reacted with Co(NO3)2·6H2O and succinic acid (L1) to yield three new metal‐organic frameworks {[Co(L1)(L2)]·(H2O)}n (1) [L2 = 2‐bis(imidazol‐1‐yl)ethane], {[Co(L1)(L3)](H2O)}n (2) [L3 = 1,4‐bis(imidazol‐1‐yl) butane], and {[Co(L1)(L4)]·(H2O)}n (3) [L4 = 1,4‐bis(2‐methyl‐imidazol‐1‐yl)butane], respectively. These complexes were synthesized under solvothermal conditions and characterized by elemental analysis, IR spectroscopy, single‐crystal and powder X‐ray diffraction, as well as thermal analyses. Interestingly, the ligands in these complexes exhibit different conformations and further cause three different configurations. Complex 1 shows a three‐dimensional (3D) framework, which is connected by two‐dimensional (2D) layer structures through hydrogen bonds. Complex 2 is a diamond structure with threefold interpenetration. Complex 3 is a 3D framework linked by hydrogen bonds like complex 1.

Correlation of Mesh Size of Metal–Carboxylate Layer with Degree of Interpenetration in Pillared-Layer Frameworks

Two porous cobal–organic frameworks showing threefold interpenetration of pillared-layer structures, constructed from two-dimensional (2D) neutral metal–carboxylate layers and neutral bis-pyridyl-bis-amide pillars, were hydro(solvo)thermally synthesized and structurally characterized by single-crystal X-ray diffraction. Compound {[Co2(thdc)2(bpda)2(DMF)]·2DMF}n (1, thdc = 2,5-thiophenedicarboxylate; bpda = N,N′-bis(4-pyridinyl)-1,4-benzenedicarboxamide) adopts a uninodal 6-connected three-dimensional (3D) framework with a {412·63}-pcu topology in which 2D rhomboid-like 44-sql Co–thdc layers are pillared by bpda ligands. While compound {[Co3(btc)2(bpda)3]·2DMF·9H2O}n (2, btc = 1,3,5-benzenetricarboxylate) is composed of a binodal (3,4)-connected 3D framework with a (63)2(64·8·10)3 topology that can be described in terms of two building subunits—a 2D porous honeycomb-like 63-hcb Co–btc layer and a bpda pillar. An in-depth analysis showed that the mesh size of the metal–carboxylate layer, in addition to the ...