Two Coordination Polymers Constructed from Pentanuclear Zinc Clusters with Triazolate and Benzenecarboxylate Ligands: Selective Gas Adsorption

2018 ◽  
Vol 71 (3) ◽  
pp. 111 ◽  
Author(s):  
Wen-Wen Zhang ◽  
Yu-Ling Wang ◽  
Ying Liu ◽  
Qing-Yan Liu

Reactions of Zn(NO3)2·6H2O with 1,2,4-triazole (Htrz) and 1,3,5-benzenetricarboxylic acid (H3BTC) or 5-sulfoisophthalic acid (5-H3SIP) afforded two coordination polymers, {[Zn5(μ3-OH)2(trz)2(BTC)2(DMF)2]·x(solvent)}n (1) and {[Zn7(trz)8(5-SIP)2(H2O)4]·4(H2O)}n (2). Compound 1 has pentanuclear [Zn5(μ3-OH)2] clusters, which are linked by the triazolate ligands to give a 2D layer. The 2D layer is further bridged by BTC3− ligands to form a 3D framework. The 3D framework of 1 has 1D channels filled by solvent molecules. Desolvated 1 shows a moderate CO2 uptake and high CO2/CH4 and CO2/N2 adsorption selectivities due to its carboxylate oxygen decorated pore environment. Compound 2 contains a rare 3D zinc-triazolate framework constructed from a pentanuclear [Zn5(trz)8] cluster wherein the five zinc atoms are arranged linearly. The 3D zinc-triazolate substructure has 1D open channels filled by 5-SIP3− ligands, which interact with the zinc-triazolate framework through Zn–O bonds, leading to a non-porous 3D structure of 2. Introduction of BTC3− into the zinc-triazolate system gave the porous structure of 1. While a variation of BTC3−, 5-SIP3− was introduced into the zinc-triazolate system yielding a non-porous structure of 2, demonstrating that the secondary ligands play an important role in the formation of the final structures.

2019 ◽  
Vol 75 (4) ◽  
pp. 443-450
Author(s):  
Guiying Zhu ◽  
Yang Lu ◽  
Guoxia Jin ◽  
Xuan Ji ◽  
Jianping Ma

Three new one- (1D) and two-dimensional (2D) CuII coordination polymers, namely poly[[bis{μ2-4-amino-3-(pyridin-2-yl)-5-[(pyridin-3-ylmethyl)sulfanyl]-1,2,4-triazole}copper(II)] bis(methanesulfonate) tetrahydrate], {[Cu(C13H12N5S)2](CH3SO3)2·4H2O} n (1), catena-poly[[copper(II)-bis{μ2-4-amino-3-(pyridin-2-yl)-5-[(pyridin-4-ylmethyl)sulfanyl]-1,2,4-triazole}] dinitrate methanol disolvate], {[Cu(C13H12N5S)2](NO3)2·2CH3OH} n (2), and catena-poly[[copper(II)-bis{μ2-4-amino-3-(pyridin-2-yl)-5-[(pyridin-4-ylmethyl)sulfanyl]-1,2,4-triazole}] bis(perchlorate) monohydrate], {[Cu(C13H12N5S)2](ClO4)2·H2O} n (3), were obtained from 4-amino-3-(pyridin-2-yl)-5-[(pyridin-3-ylmethyl)sulfanyl]-1,2,4-triazole with pyridin-3-yl terminal groups and from 4-amino-3-(pyridin-2-yl)-5-[(pyridin-4-ylmethyl)sulfanyl]-1,2,4-triazole with pyridin-4-yl terminal groups. Compound 1 displays a 2D net-like structure. The 2D layers are further linked through hydrogen bonds between methanesulfonate anions and amino groups on the framework and guest H2O molecules in the lattice to form a three-dimensional (3D) structure. Compound 2 and 3 exhibit 1D chain structures, in which the complicated hydrogen-bonding interactions play an important role in the formation of the 3D network. These experimental results indicate that the coordination orientation of the heteroatoms on the ligands has a great influence on the polymeric structures. Moreover, the selection of different counter-anions, together with the inclusion of different guest solvent molecules, would also have a great effect on the hydrogen-bonding systems in the crystal structures.


2019 ◽  
Vol 75 (5) ◽  
pp. 575-583 ◽  
Author(s):  
Yuting Bai ◽  
Meirong Han ◽  
Enxi Wu ◽  
Sisi Feng ◽  
Miaoli Zhu

Two three-dimensional (3D) CdII coordination polymers, namely poly[[di-μ-aqua-diaquabis{μ5-4,4′,4′′-[benzene-1,3,5-triyltris(oxy)]tribenzoato}tricadmium(II)] dihydrate], {[Cd3(C27H15O9)2(H2O)4]·2H2O} n , (I), and poly[[aqua{μ6-4,4′,4′′-[benzene-1,3,5-triyltris(oxy)]tribenzoato}(μ-formato)[μ-1,1′-(1,4-phenylene)bis(1H-imidazole)]dicadmium(II)] dihydrate], {[Cd2(C27H15O9)(C12H10N4)(HCOO)(H2O)]·2H2O} n , (II), have been hydrothermally synthesized from the reaction system containing Cd(NO3)2·4H2O and the flexible tripodal ligand 1,3,5-tris(4-carboxyphenoxy)benzene (H3tcpb) via tuning of the auxiliary ligand. Both complexes have been characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR spectra, powder X-ray diffraction and thermogravimetric analysis. Complex (I) is a 3D framework constructed from trinuclear structural units and tcpb3− ligands in a μ5-coordination mode. The central CdII atom of the trinuclear unit is located on a crystallographic inversion centre and adopts an octahedral geometry. The metal atoms are bridged by four syn–syn carboxylate groups and two μ2-water molecules to form trinuclear [Cd3(COO)4(μ2-H2O)2] secondary building units (SBUs). These SBUs are incorporated into clusters by bridging carboxylate groups to produce pillars along the c axis. The one-dimensional inorganic pillars are connected by tcpb3− linkers in a μ5-coordination mode, thus forming a 3D network; its topology corresponds to the point symbol (42.62.82)(44.62)2(45.66.84)2. In contrast to (I), complex (II) is characterized by a 3D framework based on dinuclear cadmium SBUs, i.e. [Cd2(COO)3]. The two symmetry-independent CdII ions display different coordinated geometries, namely octahedral [CdN2O4] and monocapped octahedral [CdO7]. The dinuclear SBUs are incorporated into clusters by bridging formate groups to produce pillars along the c axis. These pillars are further bridged either by tcpb3− ligands into sheets or by 1,4-bis(imidazol-1-yl)benzene ligands into undulating layers, and finally these two-dimensional surfaces interweave, forming a 3D structure with the point symbol (4.62)(47.614). Compound (II) exhibits reversible I2 uptake of 56.8 mg g−1 with apparent changes in the visible colour and the UV–Vis and fluorescence spectra, and therefore may be regarded as a potential reagent for the capture and release of I2.


CrystEngComm ◽  
2014 ◽  
Vol 16 (22) ◽  
pp. 4783-4795 ◽  
Author(s):  
Biswajit Bhattacharya ◽  
Debraj Saha ◽  
Dilip Kumar Maity ◽  
Rajdip Dey ◽  
Debajyoti Ghoshal

2017 ◽  
Vol 53 (35) ◽  
pp. 4748-4758 ◽  
Author(s):  
Balaram Mohapatra ◽  
Pratibha Pratibha ◽  
Sandeep Verma

This feature article outlines design strategies for modified adenine derivatives to construct discrete metal complexes, ring-expanded skeletons, coordination polymers, MOFs, and capped nanoparticles, for applications in gas adsorption, as bioimaging agents and as bioactive molecules.


2016 ◽  
Vol 09 (03) ◽  
pp. 1650043 ◽  
Author(s):  
Haolin Wu ◽  
Jie Yang ◽  
Haibiao Chen ◽  
Feng Pan

Preferentially etching either carbon or silica from silicon oxycarbide (SiOC) created a porous network as an inverse image of the removed phase. The porous structure was analyzed by gas adsorption, and the experimental results verified the nanodomain structure of SiOC. This work demonstrated a novel approach for analyzing materials containing nanocomposite structures.


2018 ◽  
Vol 74 (12) ◽  
pp. 1719-1724 ◽  
Author(s):  
Yimin Mao ◽  
Peter Y. Zavalij

Two ZnII-based coordination polymers (CPs) were synthesized by the hydrothermal method, using Zn(NO3)2·6H2O and furan-2,5-dicarboxylic acid (FDCA) in dimethylformamide (DMF) solvent, at 95 °C. Poly[tetrakis(dimethylazanium) [tetrakis(μ2-furan-2,5-dicarboxylato-κ2 O 2:O 5)dizinc(II)]], {(C2H8N)4[Zn2(C6H2O5)4]} n or {[DMA]4[ZnII 2(FDC)4]} n (DMA = dimethylazanium and FDC = furan-2,5-dicarboxylate), (1), was obtained with a 1:1 molar ratio of ZnII and FDCA. It crystallized in the monoclinic space group C2/c. Coordinated by ZnII ions, FDC2− ligands form 21 double-stranded helices propagating along the b axis. The helices are interconnected and extend laterally in the a direction, forming a two-dimensional (2D) sheet-like network. The 2D sheets are stacked along the c direction without interconnections. DMA cations are cocrystallized in (1) and are hydrogen bonded with carboxylate O atoms of the FDC2− ligands. The hydrogen-bonding pattern consists of R 2 2(4) and R 2 2(10) motifs alternating in a chain. Poly[bis(dimethylazanium) [bis(μ4-furan-2,5-dicarboxylato-κO 2:κO 2′:κO 5:κO 5)bis(μ3-furan-2,5-dicarboxylato-κO 2:κO 2′:κO 5)dizinc(II)] dimethylformamide 3.08-solvate], {(C2H8N)2[Zn2(C6H2O5)4]·3.08C3H7NO} n or {[DMA]2[ZnII 3(FDC)4]·3.08DMF} n , (2), was obtained with a 1:2 molar ratio of ZnII and FDCA. It crystallized in the monoclinic space group P21/c, forming a three-dimensional network. The pores are filled with DMA cations and DMF solvent molecules.


CrystEngComm ◽  
2020 ◽  
Vol 22 (42) ◽  
pp. 7046-7053
Author(s):  
Lingling Gao ◽  
Yongjun Bian ◽  
Yuan Tian ◽  
Yongqiang Chen ◽  
Tuoping Hu

A pictogram: the gas adsorption and magnetic properties of three Co(ii) coordination polymers constructed from 3,5-di(2′,5′-dicarboxylphenyl)benzoic acid ligand have been explored.


Processes ◽  
2019 ◽  
Vol 8 (1) ◽  
pp. 17 ◽  
Author(s):  
Raghad M. Omer ◽  
Emaad T. B. Al-Tikrity ◽  
Gamal A. El-Hiti ◽  
Mohammed F. Alotibi ◽  
Dina S. Ahmed ◽  
...  

High energy demand has led to excessive fuel consumption and high-concentration CO2 production. CO2 release causes serious environmental problems such as the rise in the Earth’s temperature, leading to global warming. Thus, chemical industries are under severe pressure to provide a solution to the problems associated with fuel consumption and to reduce CO2 emission at the source. To this effect, herein, four highly porous aromatic Schiff bases derived from melamine were investigated as potential media for CO2 capture. Since these Schiff bases are highly aromatic, porous, and have a high content of heteroatoms (nitrogen and oxygen), they can serve as CO2 storage media. The surface morphology of the Schiff bases was investigated through field emission scanning electron microscopy, and their physical properties were determined by gas adsorption experiments. The Schiff bases had a pore volume of 0.005–0.036 cm3/g, an average pore diameter of 1.69–3.363 nm, and a small Brunauer–Emmett–Teller surface area (5.2–11.6 m2/g). The Schiff bases showed remarkable CO2 uptake (up to 2.33 mmol/g; 10.0 wt%) at 323 K and 40 bars. The Schiff base containing the 4-nitrophenyl substituent was the most efficient medium for CO2 adsorption and, therefore, can be used as a gas sorbent.


2019 ◽  
Vol 109 ◽  
pp. 00101
Author(s):  
Oleksandr Topal ◽  
Iryna Holenko ◽  
Inna Diakun

The results of determination of parameters of porous structure of coal and char particles are presented. They were determined using gas adsorption method and thermal decomposition of particles in air oxygen. The porous structure parameters allow predicting char reactivity change at different temperatures as well as during conversion in accordance with Random Pore Model (RPM-model).


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