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The combination of electron-deficient viologen ligands with electron-rich POMs is a typical acceptor–donor system that has recently received much attention. Under solvothermal and hydrothermal conditions, by introducing three symmetric viologen ligands into POM-based hybrid materials, we successfully constructed four POMs–viologen inorganic–organic hybrid compounds, namely (1,3-bcbpy)2·(δ-Mo8O26) (1) (1,3-bcbpy·2Cl = 1,1′-bis(3-carboxybenzyl)-4,4′-bipyridine dichloride), {CoII(1,4-bcbpy)2(H2O)2[H2(β-Mo8O26)]}·2H2O·2CH2O (2), (1,4-bcbpy)2·(δ-Mo8O26)·2H2O (3) (1,4-bcbpy·2Cl = 1,1′-bis(4-carboxybenzyl)-4,4′-bipyridine dichloride, CH2O = formaldehyde), and {CuII(1,1-pmbby)2(H2O)[H2(β-Mo8O26)2]}·5H2O·C2H7N (4) (1,1-pmbby·2Cl = 1,1′-[1,4-phenylbis(methylene)]bis-(4,4′-bipyridine)dichloride, C2H7N = dimethylamine). These four compounds exhibit different fascinating structures, especially compound 4 is a typical metal–organic framework. Compounds 1–4 exhibit good discoloration behaviors under various external stimuli. For example, compounds 1–4 showed a positive response to the irradiation from a 300 W Xe lamp. When a positive voltage was applied to the ECD based on compounds 1–4, 1/2/3/4-ECD underwent a significant color conversion. What's more, compound 4 also showed obvious discoloration results after heating. In a word, 1–4 are multifunctional discoloration materials under different external stimuli. In addition, the coated filter paper prepared based on compound 3 can be used as a new printing material medium and can be successfully applied in erasable inkless printing and dual anti-counterfeiting. [ABSTRACT FROM AUTHOR]

This document is a contents list for the journal "Dalton Transactions: An International Journal of Inorganic Chemistry." It provides a list of research papers published in the journal in 2024. The topics covered in these papers include carbon-based photoelectrochemical sensors, catalytic dehydrogenation of n-alkanes, metal-organic frameworks, and coordination polymers. The journal aims to foster connections within the global chemistry community and welcomes contributions from scientists at all career stages and countries. One of the papers explores the regulation of thermal expansion in a specific layer through axial coordination and dimensional reduction. Another paper investigates the synthesis, structure, and magnetic properties of one-dimensional lanthanide coordination polymers. The third paper focuses on the structural engineering of hollow nanorods with high-performance peroxidase-like activity for colorimetric detection. [Extracted from the article]

The document is a contents list for the journal "Dalton Transactions: An International Journal of Inorganic Chemistry," published by The Royal Society of Chemistry. It features articles and papers on various topics, including synthetic routes and chemical structural analysis for new Pt(II) metallodrug design and the synthesis and reactivity of air stable Ni(II) complexes. The correction notice in the document acknowledges an error in the original publication of a study on the reactivity of a Lewis superacidic carborane-based compound towards Lewis bases, authored by Libo Xiang, Alexander Matler, Leibo Tan, and Qing Ye. The notice provides the correct page number for the article. [Extracted from the article]

The document is a contents list for the journal "Dalton Transactions: An International Journal of Inorganic Chemistry." It includes various articles and papers on topics such as copper complexes, lanthanide-based POMs, and coordination polymers. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document also mentions approved training courses offered by the society. The given document is a list of papers published in the journal Dalton Transactions. The papers cover a range of topics in chemistry, including catalysis, phosphors, materials synthesis, and more. Each paper is identified by its title, authors, and page number. The document also includes a correction and a retraction for two previously published papers. [Extracted from the article]

The document is a contents list for the journal "Dalton Transactions: An International Journal of Inorganic Chemistry." It includes a range of articles on various topics related to inorganic chemistry, such as electrocatalysts for water splitting, phosphors for backlight display applications, and metal-organic compounds in sensing and catalysis. The journal is published by The Royal Society of Chemistry, a leading chemistry community. The document provides a list of articles and their authors, along with images and permissions. [Extracted from the article]

Although organometallic porous polymer networks are recognized as promising heterogeneous catalysts, the relationship between ligand/monomer geometry and network parameters is usually not well understood due to the lack of atom-resolved characterization methods for the amorphous network matrix. In this work, a series of copper(II) salen-type metal complexes was synthesized, using trans- and cis-1,2-diaminocyclohexane segments, and thoroughly characterized by single-crystal X-ray diffraction and solution- and solid-state NMR spectroscopy. Terminal ethynyl groups of the complexes were then transformed into polyacetylene chains by coordination chain-growth homopolymerization, resulting in highly porous (458–655 m2 g−1) organometallic polymer networks with a copper(II) ion content of about 12 wt%. The presence of paramagnetic copper(II) moieties in these complexes and respective polymer networks required the application of tailored NMR techniques, which together with X-ray crystallography and DFT calculations of the paramagnetic NMR shifts made it possible to investigate the differences in the complex geometry in liquid, powder and crystalline form and compare it with the complex geometry in polymer networks. All prepared organometallic polymer networks were also tested as heterogeneous catalysts for styrene oxidation with uncommonly high substrate conversions and compared with their low-molecular-weight analogues. The high reusability of such heterogeneous polymer-based catalysts was also proven. [ABSTRACT FROM AUTHOR]

A thiophene-derived Schiff base ligand (E)-2-morpholino-N-(thiophen-2-ylmethylene)ethanamine was used for the synthesis of M(II) complexes, [TEM(M)X2] (M = Co, Cu, Zn; X = Cl; M = Cd, X = Br). Structural characterization of the synthesized complexes revealed distorted tetrahedral geometry around the M(II) center. In vitro investigation of the synthesized ligand and its M(II) complexes showed considerable anti-urease and leishmanicidal potential. The synthesized complexes also exhibited a significant inhibitory effect on urease, with IC50 values in the range of 3.50–8.05 μM. In addition, the docking results were consistent with the experimental results. A preliminary study of human colorectal cancer (HCT), hepatic cancer (HepG2), and breast cancer (MCF-7) cell lines showed marked anticancer activities of these complexes. [ABSTRACT FROM AUTHOR]

Two complexes {[GdCu5(GlyHA)5(H2O)7Cr(C2O4)3]·11.02H2O}n (1) and {{[GdCu5(GlyHA)5(H2O)6]μ2-[Cu(C2O4)2(H2O)]}2μ4-[Cu(C2O4)2]·15.8H2O}n (2), were obtained as outcomes of the reactions between the cationic hexanuclear {GdCu5(GlyHA)5}3+ 15-metallacrown-5 complex (where GlyHA2− = glycinehydroxamate) and the anionic oxalate complexes K3[Cr(C2O4)3] or K2[Cu(C2O4)2]. Both 1 and 2 possess polymeric 1D-chain structures according to X-ray structural analysis. As a consequence of the geometric orientations of the donor atoms in the oxalates from [Cr(C2O4)3]3−, the Cu5 mean planes of neighboring 15-metallacrown-5 units {GdCu5(GlyHA)5}3+ are angled at 75.5° to each other, which leads to formation of a zig-zag motif in the 1D-chains of complex 1. The centrosymmetric complex 2 contains two structurally different bis(oxalato)cuprate anions μ2-[Cu(C2O4)2(H2O)]2−, for one of which, coordination to two adjacent {GdCu5(GlyHA)5}3+ units leads to formation of linear 1D-chains in 2, while the second type, μ4-[Cu(C2O4)2]2−, is coordinated to four {GdCu5(GlyHA)5}3+ units, causing the cross-linking of single 1D-chains into a double-chain 1D coordination polymer. Studies of χMT vs. T data for 1 and 2 in a 2–300 K temperature range revealed the presence of both ferromagnetic and antiferromagnetic interactions amongst paramagnetic centres. The experimental χMT vs. T data for 1 were fitted using a model which takes into account exchange interactions between adjacent copper(II) ions, the Gd–Cu exchange interactions within {GdCu5(GlyHA)5}3+ units and additionally Gd–Cr exchange interactions. Fitting of the χMT vs. T data for 2 was not possible, since coordination of μ4-[Cu(C2O4)2]2− to {GdCu5(GlyHA)5}3+ led to the non-equivalence of several Cu–Cu exchange interactions within the metallacrown units and hence a superfluity of fittable parameters. Complexes 1 and 2 are the first examples of 15-metallacrown-5 complexes demonstrating a magnetocaloric effect (−ΔSM at 13 T reaches 24.26 J K−1 kg−1 at 5 K and 19.14 J K−1 kg−1 at 4 K for 1 and 2, respectively). [ABSTRACT FROM AUTHOR]

A new doubly carboxylato-bridged Co(II) dinuclear complex, [Co(bdtbpza)(NCS)]2 (1), was obtained in a satisfactory yield by employing a 'scorpionate'-type precursor, bdtbpza {bis-(3,5-di-tert-butylpyrazol-1-yl)acetate}, and was then structurally characterized. Single-crystal X-ray diffraction analysis revealed that, in 1, each Co(II) is penta-coordinated, leading to a distorted trigonal–bipyramidal geometry within the coordination environment of N3O2. Weak antiferromagnetic coupling within the Co(II) ions in 1 was found based on the isotropic spin Hamiltonian H = −J(S1·S2) for the Si = 3/2 system. For evaluating the spin density distribution and the mechanism for the magnetic exchange coupling, DFT analysis was performed, with the calculated result agreeing the experimental magnetic data. A study into electrochemical H2 evolution, involving cyclic voltammetry (CV), controlled potential electrolysis (CPE), and gas chromatographic (GC) analyses of the graphite electrode modified with the cobalt complex in a neutral aqueous solution revealed the high catalytic activity of the complex with a low overpotential toward H2O reduction. The faradaic efficiency of the catalyst was found to be 83.7% and the di-cobalt catalyst-modified electrode displayed quite an interesting H2-evolution activity compared with that of bare electrodes. These results are encouraging for the future potential application of 1 in water splitting. [ABSTRACT FROM AUTHOR]

Metal-organic cages (MOCs) are an emerging class of porous materials with promising applications. However, controlling the configuration of the cage packing, which can influence the overall porosity of the materials, remains a difficulty, as many factors can influence the cage assembly and stacking. Herein, we report a solvent strategy to fine-tune the packing configuration of a bilayer MOC, a small triangular prism cage (six Cu ions act as vertices, three nitrate ions act as pillars, and six nitrate ions act as caps) incorporated into a large triangular prism cage (another six Cu ions act as vertices, a couple of oxygen atoms act as pillars and six ligands (L1: 3,5-bis(pyridine-3-yl)-4H-1,2,4-triazole) act as a jointed cap) by the coordination between the triazole nitrogen from L1 and the inner vertex Cu ions. The involved solvents water, acetonitrile (MeCN) and N,N'-dimethylformamide (DMF) form hydrogen bonds with this bilayer MOC, resulting in three different types of packing associated with systemically tuned porosity (NTU-93: 12.2%, NTU-94: 19.3%, and NTU-95: 42.1%). Gas adsorption and breakthrough tests demonstrate that NTU-95 has potential ability for C2H2/C2H4 separation. This work not only shows a case of finely tuned packing of coordination cages, but also provides a powerful tool that may be extended to other cage families. [ABSTRACT FROM AUTHOR]

The construction of sulfur-incorporated cluster-based coordination polymers was limited and underexplored due to the lack of efficient synthetic routes. Herein, we report facile mechanochemical ways toward a new series of SFe3(CO)9-based dipyridyl-Cu polymers by three-component reactions of [Et4N]2[SFe3(CO)9] ([Et4N]2[1]) and [Cu(MeCN)4][BF4] with conjugated or conjugation-interrupted dipyridyl ligands, 1,2-bis(4-pyridyl)ethylene (bpee), 1,2-bis(4-pyridyl)ethane (bpea), 4,4'-dipyridyl (dpy), or 1,3-bis (4-pyridyl)propane (bpp), respectively. X-ray analysis showed that bpee-containing 2D polymers demonstrated unique SFe3(CO)9 cluster-armed and cluster-one-armed coordination modes via the hypervalent µ5-S atom. These S-Fe-Cu polymers could undergo flexible structural transformations with the change of cluster bonding modes by grinding with stoichiometric amounts of dipyridyls or 1/[Cu(MeCN)4]+. They exhibited semiconducting behaviors with low energy gaps of 1.55-1.79 eV and good electrical conductivities of 3.26 × 10-8-1.48 × 10-6 S cm-1, tuned by the SFe3(CO)9 cluster bonding modes accompanied by secondary interactions in the solid state. The electron transport efficiency of these polymers was further elucidated by solidstate packing, X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES), density of states (DOS), and crystal orbital Hamilton population (COHP) analysis. Finally, the solid-state electrochemistry of these polymers demonstrated redox-active behaviors with cathodically-shifted patterns compared to that of [Et4N]2[1], showing that their efficient electron communication was effectively enhanced by introducing 1 and dipyridyls as hybrid ligands into Cu+-containing networks. [ABSTRACT FROM AUTHOR]

This study focused on the design and synthesis of two Cu-based coordination polymers, [Cu2(4-dpye)(5-HSIP)(μ3-O)(H2O)2]·3H2O (Cu-CP-1) and [Cu(4-dpye)0.5(BCA)2] (Cu-CP-2), where 4-dpye = N,N′-bis(4-pyridinecarboxamide)-1,2-ethane, 5-H3SIP = 5-sulfoisophthalic acid, and HBCA = benzoic acid, by using a hydrothermal method. Single-crystal X-ray diffraction (SCXRD) study revealed that by adding various auxiliary ligands, the architectures of the Cu-CPs could be altered, yielding two distinct multinuclear Cu clusters. Moreover, the Cu-CPs can be used as urease inhibitors (UIs). In vitro experiments showed that the Cu-CPs had good urease inhibition effects with IC50 values of 0.53 ± 0.01 μM for Cu-CP-1 and 1.44 ± 0.01 μM for Cu-CP-2 and 98.48% (Cu-CP-1) and 96.27% (Cu-CP-2) inhibition of urease was achieved at a concentration of 100 μM, respectively. Furthermore, the inhibition effect of the tetranuclear Cu-CP was better than that of the binuclear Cu-CP. To better understand the potential mechanism of inhibition of the two copper complexes, we performed kinetic analysis using Lineweaver–Burk (L–B) plots in the presence of different concentrations of urea and different concentrations of inhibitors, and both Cu-CP-1 and Cu-CP-2 showed a non-competitive mode of inhibition. In addition, molecular docking analysis showed that the Cu-CPs were able to enter well into the urease binding pocket, thus interacting with key amino acid residues of urease to different degrees. Both kinetic and molecular docking studies theoretically explain and demonstrate the inhibition effect of both Cu-CPs on urease activity in vitro, which is expected to provide reasonable guidance and effective strategies for the development of novel, efficient, stable and safe CP-based UIs. [ABSTRACT FROM AUTHOR]

Coordination polymers (CPs) have been widely proven as sacrificial electrode materials for energy storage applications because of their high porosity, specific surface area and tunable structural topology. In this work, a new 2D Cu(II)-based CP, formulated as [Cu2(btc)(μ-Cl)2(H2O)4]n (CP-1) (H3btc = benzene-1,3,5-tricarboxylic acid), fabrication of copper oxide nanoparticles (CuO NPs) and its composite (CuO@CP-1) were successfully synthesized using solvothermal, precipitation and mechanochemical grinding approaches. Single-crystal X-ray analysis authenticated a two-dimensional (2D) layered network of CP-1. Further, CP-1, CuO NPs and composite were characterized by diffraction (Powder-XRD), spectroscopic (FTIR), microscopic (SEM), and thermal (TGA) techniques. The porosity and surface behavior of CP-1 and the composite were demonstrated using BET analyzer. Topological simplification of CP-1 shows a 3-c connected hcb periodic net. The photocatalytic behavior of CP-1 was examined over methyl red (MR) dye in the presence of sunlight and showed a promising degradation efficiency of 96.80%. The electrochemical energy storage properties of CP-1, CuO NPs and composite were investigated using cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD) analysis under aqueous 1 M H2SO4 electrolyte. The electrochemical results show better charge storage performance of CP-1 with a specific capacitance of 602.25 F g−1 at 1 A g−1 current density by maintaining a retention of up to 84.51% after 5000 cycles at 10 A g−1 current density. Comparative electrochemical studies reveal that CP-1 is a promising electrode material for energy storage. [ABSTRACT FROM AUTHOR]

An ethynyl-modified interpenetrated MOF material with lvt topology, [Cu2(BTEB)(NMF)2]·NMF·8H2O (compound 1, H4BTEB = 4,4′,4′′,4′′′-(benzene-1,2,4,5-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid, NMF = N-Methylformamide), was successfully synthesized by using an alkynyl-functionalized H4BTEB organic ligand under solvothermal conditions. Structural analysis shows that compound 1, consisting of a tetradentate carboxylic acid ligand and classical [Cu2(CO2)4] paddle-wheel structure building units, has a rare 4-connected lvt topology with dual interpenetrating structure, which can improve the framework stability, as well as the gas adsorption capacity and selectivity due to the restricted pore channel. According to the study of gas adsorption performance, compound 1 with a larger surface area, boasts a superior adsorption capacity for small gas molecules. Also, ideal adsorption solution theory (IAST) computational simulation shows that compound 1 has good gas adsorption selectivity for C3H8/CH4, indicating its potential application in gas separation. [ABSTRACT FROM AUTHOR]

The 3 : 1 reaction of [Cu(C2H4)n]ClO4 with 2,4-bis(2-pyridyl)pyrimidine (bpprd) in Me2CO under C2H4 afforded yellow prism crystals of the dinuclear Cu(I)–C2H4 complex [Cu2(bpprd)(η2-C2H4)2(ClO4)2] (1). The 3 : 1 reaction of [Cu(C2H4)n]NO3 with bpprd in Me2CO under C2H4 afforded yellow plate crystals of the tetranuclear Cu(I)–C2H4 complex [Cu4(bpprd)2(η2-C2H4)4(μ-NO3)2](NO3)2 (2). The 10 : 1 reaction of [Cu(C2H4)n]BF4 with bpprd in Me2CO under C2H4 afforded yellow plate crystals of the dinuclear Cu(I)–C2H4 complex [Cu2(bpprd)(η2-C2H4)2(BF4)]BF4 (3). The 3 : 1 reaction of [Cu(C2H4)n]BF4 with bpprd in Me2CO under C2H4 afforded red prism crystals of the polymeric Cu(I)–C2H4 complex {[Cu6(bpprd)4(η2-C2H4)2(μ–η2:η2-C2H4)(μ-BF4)2](BF4)4}n (4). The X-ray crystal structures of complexes 1–4 have been determined. The structural diversity of Cu(I)–C2H4 complexes bridged by bpprd with different anions was demonstrated. The 1D Cu(I)–bpprd/C2H4 coordination polymer 4 bridged by unusual μ–η2:η2-C2H4 and the μ-BF4− anion is of particular significance. Complex 1 exhibited relatively well-resolved 1H NMR signals of bpprd and C2H4 (δ = 4.97 ppm) in (CD3)2CO at 23 °C. [ABSTRACT FROM AUTHOR]

Urease inhibitors (UIs) and nitrification inhibitors (NIs) can greatly reduce nitrogen loss in agriculture soil. However, design and synthesis of an efficient and environmentally friendly dual-functional inhibitor is still a great challenge. Herein, four metal–organic salts (MOSs) based on heterogeneous conformations of the ligand N1,N1,N2,N2-tetrakis(2-fluorobenzyl)ethane-1,2-diamine (L), namely, [2HL]2+·[MCl4]2− (M = Cu, Zn, Cd, and Co), have been synthesized by the "second sphere" coordination method and structurally characterized in detail. Single crystal X-ray diffraction (SCXRD) analyses reveal that the four MOSs are 0D supramolecular structures containing [2HL]2+ and [MCl4]2−, which are connected through non-covalent bonds. Furthermore, the urease and nitrification inhibitory activities of MOSs are evaluated, showing excellent nitrification inhibitory activity with the nitrification inhibitory rate as high as 70.57% on the 28th day in soil cultivation experiment. In particular, MOS 1 shows significant urease inhibitory activity with half maximal inhibitory concentration (IC50) values of 0.89 ± 0.01 μM (0.5 h) and 1.87 ± 0.01 μM (3 h), which can serve as a dual-functional inhibitor. [ABSTRACT FROM AUTHOR]

Cu(I)-based coordination polymers (CPs) are known as efficient emissive materials providing an eco-friendly and cost-effective platform for the development of various functional materials and sensors. In addition to the nature of the metal center, organic ligands also play a crucial role in controlling the emissive properties of coordination polymers. Herein, we report on the synthesis of dithiane- and dithiolane-substituted triphenylamine ligands L1 and L2. These ligands were found to be emissive both in the solid state and in solution. In addition, these ligands exhibit solvatochromic behaviour due to the twisted intramolecular charge transfer (TICT) phenomenon. Next, coordination behaviour of these ligands was explored with Cu(I)X salts (X = Br and Cl) and four new 1D coordination polymers [{Cu(μ2-X)2Cu}(μ2-L)]n, CP1 (X = Br, L = L1), CP2 (X = Cl, L = L1), CP3 (X = Br, L = L2), and CP4 (X = Cl, L = L2) were synthesized and crystallographically characterized. The emission behaviour of all the CPs suggests ligand-centered transitions. On mechanical grinding, emission maxima (λem) for CP1 and CP2 were blue-shifted, whereas for CP3 and CP4 red-shifts were observed. All CPs were found to emit at 448 nm with increased intensity after grinding. It is supposed that grinding is responsible for a change in the spatial arrangement (dihedral angles) of the phenyl groups of triphenylamine, causing the observed emission shifts. Furthermore, the higher emission intensity after grinding suggests the occurrence of a similar phenomenon as an aggregation-induced quenching in these CPs. [ABSTRACT FROM AUTHOR]

Starting from imidazolium chlorides bearing bulky nitrogen donors, a series of four complexes, mainly [Cu (C^N)Cl]n coordination polymers were obtained directly as luminescent species by simple filtration from the aqueous reaction medium, highlighting a simple, eco-friendly, robust and reproducible synthetic procedure. Additionally, we have shown on the most efficient example that chloride could be exchanged very easily by other halides/pseudohalides (Br-, I-, NCS-, N3 -) allowing to slightly modulate the emitted colour while conserving the polymeric structure, except for azide for which a dimer was obtained. The combination of chemical analyses, of photoluminescence studies in the solid state including quantum yield measurement and X-ray diffraction on single crystals and as-synthesized microcrystalline powders highlighted that the polymeric luminescent species was indeed obtained directly by simple filtration and that no major alteration of the structure was observed upon recrystallisation. Samples of all polymeric complexes displayed remarkable stability towards air oxidation remaining unchanged upon storage for several months and partially retaining their photoluminescence properties even after a thermal treatment at 100 °C for 24 h. [ABSTRACT FROM AUTHOR]

Various 1D-coordination polymers with dinuclear rhombic {Cu2X2} cores (X = Br, I) were synthesized using a spontaneous evaporation method employing triphenylarsine (AsPh3) and six types of bidentate N-heteroaromatic co-ligands. The coordination polymers exhibited intense emission even at 298 K (quantum yield: up to 0.60), and their emission color was dependent on the N-heteroaromatic co-ligand. The emission efficiencies of these coordination polymers were higher than those of the discrete complexes with AsPh3 and monodentate N-heteroaromatic co-ligands reported in our previous work. In addition, the luminescence of these coordination polymers was more resistant to mechanical stimuli than that of the discrete ones. [ABSTRACT FROM AUTHOR]

Three coordination compounds from the reaction of copper(II) bromide with the flexible bis-tetrazole organosulfur ligand, 1,2-bis(1-methyl-1H-tetrazole-5-ylthio)ethane (bmtte) have been isolated and characterised. The identification of polymeric 2∞ Cu2Br4(bmtte) (1), trinuclear [Cu3Br4(bmtte)2] (2) and tetranuclear [Cu2Br2(bmtte)]2 (3) compounds shows that the reaction conditions have a significant influence on the structure of the complexes formed. Moreover, two polymorphs of the 2D Cu(II)-coordination polymer 1 have been isolated and these crystallise in the monoclinic C2/m (1m) and the triclinic P1¯ (1t) space groups. The thermal stabilities and behaviour in aqueous media of compounds 1–3 were investigated along with the reactivity of compound 2 with CuBr2 and KI. The solid-state reaction between mixed-valence compound 2 with KI or the direct reaction of CuI and bmtte under microwave irradiation allowed the preparation of the polymeric 2∞ Cu4I4(bmtte)2 (4). The redox behaviour of complexes 2 and 3 was analysed by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

An innovative [Cu(Hadp)2(Bimb)]n (KA@CP-S3) coordination polymer expands its dimensionality from a 1D chain to a 2D network. The topological analysis reveals that KA@CP-S3 has 2-connected uninodal 2D 2C1 topology. KA@CP-S3 has capable luminescent sensing for volatile organic compounds (VOCs), nitroaromatics, heavy metal ions, anions, disposed antibiotics (nitrofurantoin and tetracycline) and biomarkers. Intriguingly, KA@CP-S3 exhibits outstanding selective quenching of about 90.7% and 90.5% for the 125 mg dl−1 and 150 mg dl−1 strengths of sucrose, respectively, in aqueous solution along with other ranges in between. The photocatalytic degradation efficiency of KA@CP-S3 for the potentially harmful organic dye Bromophenol Blue displays 95.4%, which is the highest among the 13 dyes that were evaluated. [ABSTRACT FROM AUTHOR]

Two catecholase-like biomimetic catalysts, namely, two dinuclear copper complexes [Cu2(L1)(OH)(H2O)(EtOH)][ClO4]2 (C1) and [Cu2Ac2O(L1)ClO4] (C2) with the 2,6-bis(4-methyl piperazin-1-yl-methyl)-4-formyl-phenoxy ligand (L1) together with the mononuclear complex Cu(ClO4)2(L2) (C3) containing ligand 1,2-(C5H4N-6-OCH3-2-CH＝N)2CH2CH2 (L2), were synthesized. Their catalytic pathways were investigated and compared. The evaluation of the catalytic activity of compound C1 (and C2, C3) using the Michaelis–Menten model was represented by values of KM = 272.93 (223.02; 1616) μmol L−1 and Vmax of 0.981 (1.617; 1.689) μmol L−1 s−1. The role of water content in the solvent is also discussed. The dinuclear complexes C1 and C2 were found to be more efficient catalysts than mononuclear complex C3. The mode of catalytic action was characterized via cyclic voltammetry, spectrophotometry, and UV-Vis spectroelectrochemistry. The catalytic mechanism of 3,5-di-tert butyl catechol oxidation in the presence of oxygen was proposed. The reaction circle was proved by the confirmation of the chemical reversibility of complex reduction. The advantage of the in situ spectroelectrochemical measurement enabled to control the reduction of quinone formed by the chemical reaction of catechol with oxygen in solution. At this step, the simultaneous change in the absorption spectrum indicated a change in the copper redox state of the catalyst. [ABSTRACT FROM AUTHOR]

Porous isomers constructed from the same building blocks but different topology break the general preferred coordination rule of organic linkers and metal nodes, representing an invaluable opportunity for enriching their pore chemistry. Herein, a new group of porous isomers (termed as NTU-69 and NTU-70) was prepared from a C2v symmetric diimidazole–dicarboxylate ligand and mononuclear Cu ion. The structural differences arise from the different rotation configuration of the sp2 bond in the ligand, leading them to exhibit completely different topologies of unc (NTU-69) and sod (NTU-70) as well as framework rigidness. This rotation configuration of the sp2 bond can be controlled by the different acidity of the synthetic solution and the metal/ligand ratio. Gas adsorption and IAST selectivity show that NTU-70 features high potential for CH4 purification from C2H4, C2H6, C3H6 and CO2 mixtures at room temperature. The insight from this work establishes a new bridge between the ligand design and controlled construction of porous isomers. [ABSTRACT FROM AUTHOR]

This document is a back cover of an article titled "Diversity of oxidation state in copper complexes with phenolate ligands" published in the journal Dalton Transactions: An International Journal of Inorganic Chemistry. The article discusses the progress made in the redox chemistry of Cu-phenolate complexes, including the discovery of various oxidation states such as Cu II -phenoxyl radical complexes, Cu III -phenolate, Cu I complexes with phenoxyl radicals, and Cu IV -phenolate complexes. The article focuses on the correlation between geometric and electronic structures of these complexes. The article also mentions the authors of the research, Tomoyuki Takeyama and Yuichi Shimazaki, and their affiliations at Sanyo-Onoda City University and Ibaraki University in Japan. [Extracted from the article]

With the aim to elaborate novel and inexpensive sulphur-rich materials featuring unusual network architectures, the coordination chemistry of the tetradentate thiaheterocycle 1,2-di(1,3-dithian-2-yl)ethane L1 ligand toward CuX and HgX2 salts was investigated. When L1 is reacted with CuI in a 1 : 1 ratio, a two-dimensional CP [{Cu(μ2-I)2Cu}(μ2-L1)]n (CP1) is formed, in which two out of four S atoms of L1 remain non-coordinated. Upon treatment of L1 with CuI in a 1 : 2 ratio, [{Cu(μ2-I)2Cu}(μ4-L1)]n (CP2) is obtained, in which each S atom of L1 coordinates to one copper centre forming a 2D layer. Raising the ligand-to-CuI ratio to 1 : 4 affords the 2D material [{Cu(μ4-I)(μ2-I)Cu}2(μ4-L1)]n (CP3), in which [Cu(μ4-I)(μ2-I)Cu]n ribbons are interconnected through μ4-bridging L1 ligands. Upon the reaction of L1 with CuBr in a 1 : 2 ratio, a 2D CP [{Cu(μ2-Br)}2(μ2-L1)(μ4-L1)0.5]n (CP4) is formed at room temperature and a 2D CP [{Cu(μ2-Br)}2(μ4-L1)]n (CP5) is obtained in refluxing propionitrile. In CP4 and CP5 Cu atoms are bridged by a single μ2-Br ligand giving rise to [Cu(μ2-Br)Cu]n ribbons but CP4 differs from CP5 from the metal to ligand ratio and the presence of non-coordinated S atoms. Employing a 1 : 3 ratio, a 1D ribbon [{Cu(μ2-Br)}3(MeCN)(μ4-L1)]n (CP6) is generated, that contains both tetrahedral and trigonal copper atoms. CP6 also presents two different L1 ligands that differ by the coordination mode of the sulphur atoms (S acting as 2 or as 4 electron-donor). With CuCl, a 2D network [{Cu(μ2-Cl)2Cu}(μ4-L1)]n (CP7) is generated. L1 coordinates also on HgX2 salts to yield CPs whose architecture depends on the ligand-to-metal ratio. The meander-shaped 1D CP [(HgI2)(μ2-L1)]n (CP8) and the linear 1D ribbons of CP9 and CP12 [(HgX2)(μ2-L1)]n (X = Br, Cl) result from treatment with L1 in a 1 : 1 ratio. In the case of HgBr2, using a 2 : 1 metal-to-ligand ratio, 1D polymeric [{BrHg(μ2-Br)2HgBr}(μ2-L1)] (CP10) is produced. HgI2 and HgBr2 have also been reacted with 2-methyl-1,3-dithiane L2 yielding the molecular complexes [{IHg(μ2-I)2HgI}(κ1-L2)2] (D1) and [HgBr2(κ1-L2)2] (M1). Two heterometallic 1D materials [{IHg(μ2-I)2HgI(μ2-I)2{Cu(RCN)2}2(μ2-L1)]n (CP13) and (CP14) result from the treatment of CP1 with HgI2 in MeCN or EtCN. Performing the reaction of CP1 with HgBr2 in acetonitrile produces the zwitterionic 2D material [Cu(MeCN)}(HgIBr2)(μ2-L1)1.5]n (CP15). [ABSTRACT FROM AUTHOR]

A new coordination polymer based on the sulphate-capped pentamolybdate unit has been synthesized from the reaction of {Mo3S7Br6}2- with copper(II) bromide and pyridine, in DMF. The as-synthesized compound, formulated as [CuII(C5H5N)4]3[{Mo5VIO15(SO4)2}{CuII(C5H5N)3(DMF)(H2O)}][Mo5VIO15(SO4)2]·2DMF (1), crystallizes in the monoclinic space group of P21/c. This compound has a one-dimensional double-chain coordination polymeric structure, composed of the pentameric {Mo5VIO15(SO4)2} and the {CuII(C5H5N)4} units, and has been characterized in the solid-state with single-crystal and powder X-ray diffraction, infrared and optical spectroscopy, as well as thermal and magnetic studies. Due to its unique arrangement, the compound is observed to be nanoporous in nature, occupied by a co-crystallized DMF molecule. Surface area measurements confirm the presence of nano-sized pores within the compound. Variable temperature P-XRD studies show the framework to be stable up to a temperature of at least 100 °C. Due to its rigid framework and the presence of nano-sized pores, the compound was extensively studied as a catalyst for oxidative desulphurization of model oil and commercial diesel. The compound not only shows excellent performance for the removal of recalcitrant sulphur components, such as dibenzothiophene (DBT) in fuel oil (~100% removal), but is also observed to show excellent turn-over-numbers, regeneration, and reproducibility during the catalytic process. [ABSTRACT FROM AUTHOR]

This study was focused on the activation of the C＝P bond via reactions of Ph2C＝P-PtBu2 (1) with 1,6-hexanediol and selected dithiols (1,4-butanedithiol, 1,4-benzenedithiol and 1,4-benzenedimethanethiol). These reactions proceed according to a 1,2-addition mechanism, providing new compounds with formulas {(Ph)2(H)C-P-PtBu2}{μ2-(O-(CH2)6-O)}{tBu2P-P-C(H)(Ph)2} (2), {(Ph)2(H)C-P-PtBu2}{μ2-(S-(CH2)4-S)}{tBu2P-P-C(H)(Ph)2} (3a), {(Ph)2(H)C-P-PtBu2}{μ2-(S-C6H4-S)}{tBu2P-P-C(H)(Ph)2} (3b), and {(Ph)2(H)C-P-PtBu2}{μ2-(S-CH2-C6H4-CH2-S)}{tBu2P-P-C(H)(Ph)2} (3c). Next, the reactions of 3a and 3c with metal chlorides led to the growth of desired coordination polymers of copper(I) and silver(I). All the obtained compounds remained stable under atmospheric conditions. [ABSTRACT FROM AUTHOR]

Two series of heterometallic LnIII–CuII compounds containing a butterfly-like tetranuclear metal core were synthesized and characterized by X-ray diffraction and magnetometry. The structures of the new compounds were shown to depend on the nature of the hydroxide used for the synthesis. The reactions of copper(II) and lanthanide(III) salts with Hpiv (Hpiv is trimethylacetic acid) and LiOH in a MeCN–EtOH mixture afford the molecular complexes [Ln2Cu2(μ3-OH)2(piv)8(H2O)4]·4EtOH (1Ln, Ln = Gd, Tb, Dy, Ho, Yb), whereas the similar reactions using NaOH instead of LiOH give the 1D coordination polymers [Na2Ln2Cu2(μ3-OH)2(piv)10(EtOH)2]·EtOH (2Ln, Ln = Gd, Tb, Dy, Ho, Yb). According to ac susceptibility measurements, the DyIII–CuII compounds (1Dy and 2Dy) exhibit slow relaxation of magnetization indicative of single-molecule magnet (SMM) behavior. In the series of YbIII–CuII compounds, only complex 2Yb shows frequency-dependent out-of-phase ac susceptibility signals. This is the first reported example of carboxylate-based YbIII–CuII compound displaying slow magnetic relaxation. [ABSTRACT FROM AUTHOR]

First examples of copper(I) complexes with 2-(alkylsulfanyl)pyrimidine ligands have been synthesized. Reactions of copper(I) iodide with 2-(methylsulfanyl)pyrimidine (L1) in various metal-to-ligand molar ratios in MeCN afford a ladder-type coordination polymer [Cu2L1I2]n with polymeric chains built from double-stranded (Cu2I2)n ribbons supported on both sides by μ2-N,S-L1 molecules. Although the second ligand, 2-(ethylsulfanyl)pyrimidine (L2), differs from L1 only by a methylene group, its reactions with copper(I) iodide in MeCN yield not only a congenerous coordination polymer, [Cu2L2I2]n , but also [CuL2I]n , in which a similar (Cu2I2)n ribbon is decorated by N-monodentate L2 molecules. Absorption spectra of all compounds represent an interplay of metal + iodine-to-ligand charge transfer (XMLCT) and ligand-centered (LC) and cluster-centered (CC) transitions, while the emission occurs from the excited states of XMLCT nature. The luminescence of [Cu2L1I2]n and [Cu2L2I2]n is blue-shifted and greatly enhanced in comparison with that of [CuL2I]n (quantum yields: 89% and 68% for [Cu2L1I2]n and [Cu2L2I2]n vs. 23% for [CuL2I]n at 77 K), which can be associated with a more rigid μ2-N,S coordination of 2-(alkylsulfanyl)pyrimidine ligands in [Cu2L1I2]n and [Cu2L2I2]n leading to a less distorted T1 state. [ABSTRACT FROM AUTHOR]

The heterogeneous reaction between copper(I) halide and pyridine derivative ligand in a suspension conveniently afforded luminescent copper(I) complexes. The progress of the reaction was confirmed by powder X-ray diffraction (PXRD) and thermogravimetric (TG) measurements. The structure of the obtained complexes was clarified by comparison with the X-ray analysis of a single crystal obtained by the homogeneous reaction in a solution. The reaction was affected by the type of solvent and substituents on the pyridine ligand. The reaction proceeded quantitatively, not depending on copper(I) halide, when ethyl acetate and 3-bromopyridine were used as the solvent and ligand, respectively. X-ray analysis of the single-crystals obtained by the corresponding reaction in solution revealed that the reaction in suspension afforded the same stair-shaped quasi-one-dimensional structure. The obtained copper(I) complex powders displayed luminescence, which was attributed to the halide/metal-to-ligand charge transfer (XMLCT), as elucidated by crystal orbital distribution and principal component of excitation based on density functional theory (DFT) calculations. [ABSTRACT FROM AUTHOR]

Nanofibers of a copper(II)-based coordination polymer [Cu(HBTC)(H2O)3] were synthesized via a microwave-assisted hydrothermal process, while macroparticles and bulk crystals were prepared via a hydrothermal method. X-ray analysis revealed that this compound possesses one-dimensional zig-zag chains, in which the coordination polyhedron of the copper(II) center is a five-coordinate distorted square-pyramid. The width of the as-prepared nanofibers was about 150 nm, while the size of the macroparticles was about 200 μm. The antibacterial activities of the nanofibers and macroparticles against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were evaluated by determining the minimal inhibitory concentration (MIC), the growth curve of the bacteria and the bacterial reduction assay. The nanofibers showed higher antibacterial performance as compared with macroparticles, commercial copper nanoparticles, and pure ligands alone. The bacteriostatic rates of nanofibers and macroparticles were up to 99.9% and 96.7% against E. coli, while 99.1% and 96.2% against S. aureus, respectively, when the concentration was 250 μg mL−1. The synergistic antibacterial mechanism was also proposed based on the generation of reactive oxygen species (ROS) and the release of Cu2+ ions. [ABSTRACT FROM AUTHOR]

By employing enantiomerically pure mono-bidentate N-donors (LR/LS) as chiral bridging ligands to react with Cu(ClO4)2(H2O)6 in CH3CN–DMF mixed solvent, respectively, a pair of ionic one-dimensional (1D) Cu(II) chain enantiomers formulated as {[CuLR(CH3CN)(DMF)H2O](ClO4)2}n/{[CuLS(CH3CN)(DMF)H2O](ClO4)2}n (D-1/L-1) were isolated and structurally characterized, where LR/LS = (−)/(+)-4,5-pinenepyridyl-2-pyrazine. They crystallize in the noncentrosymmetric (NCS) P212121 space group of an orthorhombic system due to the introduction of chiral LR/LS, and the ClO4− groups as counteranions reside in crystal lattices, thus leading to charge separation with large dipole moments in their molecular structures. Based on crystal samples, investigation on their nonlinear optical (NLO) behaviors showed that D-1 and L-1 display simultaneously much larger second- and third-harmonic generation (SHG and THG) responses than their analogues based on the same chiral N-donors (LR/LS) and Cu(NO3)2(H2O)3 with NO3− acting as the coordination group to bind Cu(II) ions. The SHG intensities of D-1/L-1 are 0.62/0.60 × KDP (KH2PO4), and THG intensities of D-1/L-1 are 238/228 × α-SiO2. Our finding indicates that coordination polymers (CPs) with charge separation and NCS structures, i.e., ionic CPs with NCS arrangements are the ideal NLO crystalline materials for the simultaneous observation of large SHG and THG responses, thus providing a new approach to obtain NLO-active CP crystalline materials with high-performance SHG and THG responses. [ABSTRACT FROM AUTHOR]

A 2-D copper(II)-based coordination polymer, [Cu(SCN)(hmp)]n CP (1), was crystallized via the slow evaporation method after the reaction of CuSO4·5H2O, 2-pyridinemethanol (hmpH), sodium thiocyanate and sodium hydroxide in water for functional applications. CP (1) was characterized via elemental analysis, FTIR, PXRD, magnetic, EPR, crystallographic and TGA studies. The crystal structure and EPR data confirmed a square pyramidal geometry around the Cu(II) ions. The topological analysis revealed that CP 1 has a {6^3} point symbol with a [6.6.6] extended point symbol and 3-c net, uninodal net having hcb and Shubnikov hexagonal plane net/(6,3) type of uncommon topology. The magnetic studies suggested the strong antiferromagnetic nature of CP (1). The fluorescence sensing property of CP (1) was investigated with different nitro aromatic compounds and hazardous metal ions. CP (1) demonstrated high selectivity and sensitivity towards nitrobenzene, even in the presence of other competitive nitro aromatics. In addition, CP (1) showed excellent selectivity and sensitivity toward Fe3+ over other metal ions. The possible detection mechanisms were proposed employing UV-visible and fluorescence spectroscopy and DFT calculations. CP (1) also showed excellent recyclability towards both analytes, and its initial intensity was almost regained after several washings. Moreover, CP (1) acted as an excellent adsorbent material for natural dyes with different charges and sizes, i.e., methylene blue (MB), methyl orange (MO) and Rhodamine-B. Furthermore, CP (1) was utilized repeatedly for the effective adsorption of MB from wastewater without significant loss in its adsorption capacity. Hence, the present CP (1) was designed to relate coordination chemistry with various functional applications of interest. [ABSTRACT FROM AUTHOR]

The electrostatic self-assembly reaction of the [Cu(HL)]2+ cation, where HL = 2-(2-aminoethylamino) ethanol, and the N3− or [Fe(CN)6]4− anion leads to the formation of two coordination polymers with the general formula of [Cu6(μ1,1-N3)6(μ1,3-N3)2(μ1,1,3-N3)2(μ1,1,1,3-N3)2(HL)2]n (1) and {[Cu(HL)]2[Fe(CN)6]·H2O}n (2), respectively. The resulting compounds have been structurally characterized by a single-crystal X-ray diffraction technique. Compound 1 possesses a rare 3D structure. It contains centrosymmetric hexanuclear repeating units, which act as six-connected nodes in the final network and copper(ii) ions are joined together by azide anions with four different types of bridging modes, μ1,1, μ1,1,3, μ1,1,1,3, and μ1,3. The structure of compound 2 is a 2D heterometallic CuII/FeII layer in which the [Cu(HL)]2 nodes and the octahedral [Fe(CN)6]4− linkers are joined by μ2- and unusual μ3-CN bridging modes. Detailed static and dynamic magnetic analyses of 1 reveal a dominant ferromagnetic intracluster interaction and a ferromagnetic 3D ordering transition below Tc = 5 K. The variable temperature magnetic susceptibility measurements of compound 2 show a very weak ferromagnetic coupling between the nearest Cu(ii) ions. Also, EPR spectroscopy of these compounds has been investigated in the solid state. Nanocrystals of compound 2 have also been synthesized by a sonochemical process under different reaction conditions. The results show that the crystallinity degree and uniform distribution of nanosheets are inversely dependent on the irradiation time. [ABSTRACT FROM AUTHOR]

A series of metal organic coordination polymers (MOCPs) of silver(I) and copper(II) coordinated with a novel multifunctional semi-rigid sulfonyl ligand with different anion templates and oxidation states were designed for the first time. In addition, their atomically precise molecular structure was determined by single crystal X-ray diffraction analysis. In comparison, the topology of silver(I)-based MOCPs is affected significantly by different anion templates. The coordination modes are quite different with the anions varying: linear for ClO4−, trilateral for CO2CF3−, and tetrahedral for CO2C2F5−. Due to the difference of electron configurations between Ag(I) and Cu(II), the coordinated configuration of the metal center is also different. While the coordinated configuration of Cu(II) center tends to be placed in an octahedron. Furthermore, for the copper(II) MOCPs, the oxidation state of the L ligand also plays an important role. When the N atoms in L were oxidized, the coordination mode of Cu(II) became tetrahedral with Cu(II) stuck on the bottom of the conventional octahedral mode. In general, it is an effective and controllable strategy to mediate the coordination mode and aggregation of supramolecular assembly-based MOCPs through the combination of a multifunctional organic ligand and its corresponding oxidation state design; elaborate metallic species and electron configuration selection; and suitable anion template introduction to generate multiform and hierarchical non-covalent bond interactions including π–π interactions and hydrogen bond formation that afford their coordination mode diversity. [ABSTRACT FROM AUTHOR]

At different reaction temperatures, using Cu(NO3)2·3H2O to react with enantiomerically pure N-donor ligands (LS/LR), respectively, two pairs of chiral one-dimensional (1D) CuII chain enantiomers formulated as [Cu(μ2-NO3)(NO3)(LS)]n/[Cu(μ2-NO3)(NO3)(LR)]n (S-1-Cu / R-1-Cu , formed at 40 °C with an NO3− group as a sole bridging ligand) and [Cu(μ2-LS)(NO3)2]n/[Cu(μ2-LR)(NO3)2]n (S-2-Cu / R-2-Cu , formed at 25 °C with LS or LR as a bridging ligand) were prepared, where LS/LR = (+)/(−)-4,5-pinenepyridyl-2-pyrazine. Interestingly, such a disparity in bridging ligands leads not only to their distinct structural features but also to their completely different magnetic couplings together with a large difference in their nonlinear optical responses. S-1-Cu with a 1D helical structure shows weak ferromagnetic coupling between CuII ions, while S-2-Cu with a 1D stairway-like structure presents weak antiferromagnetic coupling. In particular, they simultaneously possess both second- and third-harmonic generation (SHG and THG) responses in one molecule with large strength differences. More remarkably, S-1-Cu exhibits a very large THG response (162 × α-SiO2), which is 22.5 times that of S-2-Cu , and the SHG strength of S-1-Cu is more than 3 times that of S-2-Cu. This work demonstrates that reaction temperature has a great impact on the self-assembled structures of coordination polymers and subsequently results in their large performance differences. [ABSTRACT FROM AUTHOR]

A novel coordination polymer with the chemical formula [Cu4Br(CN)(mtz)2]n (mtz = 5-methyl tetrazole) (1), has been synthesized under solvothermal conditions and characterized by elemental analysis, infrared (IR) spectroscopy, thermal gravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Interestingly, the Cu(i), CN− and mtz− in compound 1 are all generated from an in situ translation of the original precursors: Cu2+, acetonitrile and 1-methyl-5-mercapto-1,2,3,4-tetrazole (Hmnt). The in situ ring-to-ring conversion of Hmnt into mtz− was found for the first time. Structural analysis reveals that compound 1 is a novel 3D tetrazole-based Cu(i) coordination polymer, containing both metal halide cluster Cu6Br2 and metal pseudohalide cluster Cu2(CN)2 secondary building units (SBUs), which shows an unprecedented (3,6,10)-connected topology. Notably, a pseudo-porphyrin structure with 16-membered rings constructed by four mtz− anions and four copper(i) ions was observed in compound 1. The fluorescence properties of compound 1 were investigated in the solid state and in various solvent emulsions, the results show that compound 1 is a highly sensitive naked-eye colorimetric sensor for NB and 2-NT (NB = nitrobenzene and 2-NT = 2-nitrotoluene). [ABSTRACT FROM AUTHOR]

The present study focuses on the long-range structural changes that occur in the porous coordination polymer Cu2(pzdc)2(bpy) (pzdc = pyrazine-2,3-dicarboxylate, bpy = 4,4'-bipyridine), also known as CPL-2, upon adsorption of CO2 at 25 °C and up to 7 atm. The structural data were gathered using in situ diffraction studies. CPL-2 exhibited an unexpected hysteretic adsorption-desorption process. The onset of hysteresis occurs at a pressure where full occupancy of the volume of the CPL-2 galleries is achieved while the framework retains a structure similar to what is observed under ambient conditions. Moreover, the onset occurs at a CO2 partial pressure larger than 2 atm and could be related to a combination of adsorbate-adsorbent interactions and forces exerted onto the CPL-2 framework. Pore volumes estimated from fits of the Dubinin-Astakhov isotherm model against the CO2 desorption data gathered at 25 and -78.5 °C, respectively, provided further evidence of the aforementioned CPL-2 framework changes. These findings are of relevance to the understanding of adsorption processes in metal organic frameworks or coordination polymers under conditions that are of relevance to gas capture at industrial scale. [ABSTRACT FROM AUTHOR]

Nanoparticles of a copper-based layered coordination polymer, STAM-2, have been prepared via an ultrasound mediated transformation from a layered metal-organic framework, STAM-1. The structure of the material was then solved using pair distribution function analysis to identify the structural units present and the final structural model refined against the pair distribution function data. [ABSTRACT FROM AUTHOR]

An unusual copper(ii) coordination polymer {[Cu(tmtz)(H2O)4][Cu2(tmtz)2(sip)2]·4H2O}n (1) (tmtz = 1,4-bis(1,2,4-triazol-1-ylmethyl)-2,3,4,5-tetramethylbenzene, sip = 5-sulfoisophthalate) is synthesized by the hydrothermal reaction. X-Ray structural analysis shows that 1 is comprised of two distinct and crystallographically independent polymeric motifs polythreading together. The first motif of 1 is an unusual (3,5)-connected 3D anionic network [Cu2(tmtz)2(sip)2]. The second motif in 1 is the [Cu(tmtz)(H2O)4]n 1D cationic chain. A polythreading array formed by a (3,5)-connected 3D anionic network and 1D cationic chains. The catalytic performance exhibits that 1 is active as a catalyst for the degradation of methyl orange. The thermal analysis is also observed. [ABSTRACT FROM AUTHOR]

Two copper(ii) coordination polymers, viz. [Cu2(OAc)4(μ4-hmt)0.5]n (1) and [Cu{C6H4(COO−)2}2]n·2C9H14N3 (2), have been synthesized solvothermally and characterized. The solid-state structure reveals that 1 is an infinite three-dimensional (3D) motif with fused hexagonal rings consisting of Cu(ii) and hmt in a μ4-bridging mode, while 2 is an infinite two dimensional (2D) motif containing Pht−2 in a μ1-bridging mode. CP 1 has a two-fold interpenetrated diamondoid network composed of 4-connected sqc6 topology with the point symbol of {66}, while 2 has a Shubnikov tetragonal plane network possessing a 4-connected node with an sql topology with a point symbol of {44·.62}-VS [4·4·4·4·*·*]. Both CPs 1 and 2 serve as efficient catalysts for CO2-based chemical fixation. Moreover, 1 demonstrates one of the highest reported catalytic activity values (%yield) among Cu-based MOFs for the chemical fixation of CO2 with epoxides. 1 shows high efficiency for CO2 cycloaddition with small epoxides but its catalytic activity decreases sharply with the increase in the size of epoxide substrates. The catalytic results suggested that the copper(ii) motif-catalyzed CO2 cycloaddition of small substrates had been carried out within the framework, while large substrates could not enter into the framework for catalytic reactions. The high efficiency and size-dependent selectivity toward small epoxides on catalytic CO2 cycloaddition make 1 a promising heterogeneous catalyst for carbon fixation and it can be used as a recoverable stable heterogeneous catalyst without any loss of performance. The solvent-free synthesis of the cyclic carbonate from CO2 and an epoxide was monitored by in situ FT-IR spectroscopy and an exposed Lewis-acid metal site catalysis mechanism was proposed. [ABSTRACT FROM AUTHOR]

A new one dimensional coordination polymer of copper(ii), [Cu4(L)2(μ2-1,1-OAc)2(μ2-1,3-OAc)4]n (1), has been synthesized and characterized by spectroscopic methods and single crystal X-ray analysis [HL = (E)-N′-(phenyl(pyridin-2-yl)methylene)isonicotinhydrazide, OAc = acetate anion]. The coordination polymer contains two kinds of Cu(ii) dimers which are connected by two types of acetate (μ2-1,1- and μ2-1,3-) bridging groups. The ditopic isonicotinhydrazone ligand coordinates to the Cu1 center through the N2O-donor set and connects to the Cu2 center by a pyridine group of the isonicotine part. The EPR and magnetic susceptibility measurements confirm the existence of two kinds of Cu(ii) dimers. The intradimer isotropic exchange was estimated to be +0.80(1) cm−1 for the ferromagnetic Cu1…Cu1 dimeric unit and −315 (1) cm−1 for the antiferromagnetic Cu2…Cu2 dimeric unit. [ABSTRACT FROM AUTHOR]