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Proton-conductive materials have attracted increasing attention because of their broad explorations in chemical sensors, water electrolysis, fuel cells, and biological systems. Especially, metal-organic frameworks (MOFs) have been demonstrated to be extremely promising candidates as proton-exchange membrane (PEM) fuel cells. Compared with other configurations, MOFs with one-dimensional (1D) channels have the characteristics of enhancing the host-guest interaction and promoting the anisotropic motion of proton carriers in restricted volume, which are beneficial for acquiring rich proton sources and forming successive hydrogen bonds to improve proton conductivity. We are endeavored to screen and find a helical three-dimensional (3D) framework InOF-1, namely, [In2(OH)2(BPTC)]·6H2O (BPTC4- = 3,3',5,5'-biphenyl tetracarboxylate), as a typical 1D-channel MOF, which is pristinely grafted with spirally distributed -OH groups on the channel surface. Accompanied by an aliovalent substitution Ni(II) for In(III), isostructural NiOF-1 ([Ni2(BPTC)(HCOOH)2]·3H2O) is successfully prepared and massive formic acids are anchored at interior walls, which are interacted with adsorbed water molecules via the formation of stronger O-H···O bonds. This interaction between host-guest molecules and dynamics of lattice water has already led to a remarkable conductivity of InOF-1 (σ = 7.86 × 10-3 S/cm at 328 K under 95% RH). The synergistic effect of the acidic-modified nanowall, contracted volume, and enhanced adsorption of water molecules in the NiOF-1 channel contributes to a high conductivity value of 3.41 × 10-2 S/cm (at 328 K under 95% RH). Moreover, the proton conduction mechanism is further visually presented by molecular dynamic (MD) simulation. In contrast to InOF-1, aliovalent-substituted and acidic-modified NiOF-1 has a stronger host-guest interaction and more abundant hydrogen-bond networks, resulting in shorter proton migration distances and more frequent proton hopping, in agreement with the experimental results.

Titanium-oxide or polyoxotitanate clusters are a new type of inorganic host materials that can encapsulate inorganic molecules or ions. We report herein a (NH4)4(enH2)[Ti18O27(PhCOO)24(en)9] molecular cage (Ti18) that encapsulates an entire organic ethylenediamine (en) ion. A thorough investigation has revealed the extraordinary versatility of en. Besides being a guest cation, it also functions as chelating and bridging ligand. It balances the charge of the negative Ti18 cage and facilitates the deprotonation of benzoic acid at the early stage of the reaction as well. DFT calculation and a derivative of Ti18 with open sites at its equatorial position shed further light on the formation mechanism. Ti18 strongly absorbs visible light as a result of en coordination, and it exhibits superior photocatalytic activity compared to anatase TiO2.

A straightforward global layout of carbon capture, utilization and storage (CCUS) is imperative for limiting global warming well below 2 °C. Here, we propose a cost-effective strategy for matching carbon sources and sinks on a global scale. Results show 3,093 carbon clusters and 432 sinks in 85 countries and regions are selected to achieve 92 GtCO2 mitigation by CCUS, 64% of which will be sequestered into sedimentary basins for aquifer storage and 36% will be used for CO2-EOR (enhanced oil recovery). Of the identified source–sink matching, 80% are distributed within 300 km and are mainly located in China, the United States, the European Union, Russia and India. The total cost is ~0.12% of global cumulative gross domestic product. Of countries with CO2-EOR, 75% will turn into profitable at the oil price over US$100 per barrel. These findings indicate our proposed layout is economically feasible. However, its implementation requires global collaboration on financial and technological transfer. Carbon capture, utilization and storage (CCUS) will be required to meet climate targets. An economically feasible global CCUS layout can be achieved by capturing the carbon sources in 85 regions and mitigating with 59 GtCO2 sequestration and aquifer storage and 33 GtCO2-enhanced oil recovery.

The design and utilization of dual sites for synergistic catalysts has been recognised as an efficient method towards high-efficiency catalysis in the cyanosilylation of aldehydes, which gives key intermediates for the synthesis of a number of valuable natural and pharmaceutical compounds. However, most of the reported dual-site catalysts for this reaction were homogeneous, accompanied by potential deactivation through internal complexation of the dual sites. Herein, by the rational selection of an uncoordinated tertiary nitrogen based tricarboxylic ligand (tris[(4-carboxyl)-phenylduryl]amine, H3TCBPA), a new three-dimensional calcium-based metal-organic framework (MOF), Ca3(TCBPA)2(DMA)2(H2O)2 (1, where TCBPA = ionized tris[(4-carboxyl)-phenylduryl]amine and DMA = N,N-dimethylacetamide), possessing accessible dual catalytic sites, Lewis-basic N and Lewis-acidic Ca, has been designed and constructed by a one-pot solvothermal reaction. As expected, 1 is capable of dually and heterogeneously catalysing the cyanosilylation of aldehydes at room temperature, and can be reused for at least 6 runs with a maximum turnover number (TON) of 1301, which is superior to most reported cases. Additionally, 1 shows CO2 adsorption ability and conversion with epoxides, which is beneficial for the establishment of a sustainable society.

The only feasible access to non-face-centered cubic (FCC) copper was by physical vapor deposition under high vacuum. Now, non-FCC copper is observed in a series of alkynyl-protected Cu53 nanoclusters (NCs) obtained from solution-phase synthesis. Determined by single-crystal X-ray crystallography, the structures of Cu53 (C≡CPhPh)9 (dppp)6 Cl3 (NO3 )9 and its two derivatives reveal an ABABC stacking sequence involving 41 Cu atoms. It can be regarded as a mixed FCC and HCP structure, which gives strong evidence that Cu can be arranged in non-FCC lattice at ambient conditions when proper ligands are provided. Characterization methods including X-ray absorption fine structure, XPS, ESI-MS, UV/Vis, Auger spectroscopy, and DFT calculations were carried out. CuII was shown to successively coordinate with introduced ligands and changed to CuI after bonding with phosphine. The following addition of NaBH4 and the aging step further reduced it to the Cu53 NC.

Discrete supertetrahedral clusters of metal chalcogenides are rare because of the difficulty involved in meeting global charge matching between the negative charge of the skeleton and counterion. We present herein the third type of a discrete chalcogenide cluster with a double T3 structure in the compound (HDBN)6[In20S33(DBN)6] (DBN = 1,5-diazabicyclo [4.3.0]-5-nonene), the anion of which features quasi-D3 symmetrical double-T3 In20S33 supertetrahedra with six cornered indium atoms coordinated by DBN molecules. DFT theory calculations of the interaction between host and guest show that this compound may have high kinetic stability and low photoelectric reactivity.

Exploring efficient and stable oxygen evolution reaction (OER) catalysts with earth-abundant elements has been an urgent task in water splitting. Metal-organic frameworks (MOFs), possessing abundant active metal sites and tunable porous crystalline structures, are promising as OER catalysts. In this paper, a MOF based on benzotriazole-5-carboxylate (Co3-btca) that contains unsaturated coordinated metal centers and a 1D channel was selected to act as an OER catalyst. To optimize the OER performance, isostructural bimetallic and trimetallic frameworks were obtained by doping with Fe and/or Ni ions. The optimized Co2.36Fe0.19Ni0.45-btca possesses the lowest overpotential of 292 mV at 10 mA cm-2 and a small Tafel slope of 72.6 mV dec-1. The enhanced catalytic performance could be attributed to the synergistic effect between the unsaturated coordinated Co, Fe and Ni sites, which are beneficial for the nucleophilic attack of OH- forming adsorption intermediates.

The discovery of has inspired new interest in studying doubly heavy baryons. In this study, the weak decays of a doubly charmed baryon to a light baryon and a charm meson (either a pseudoscalar or a vector one) are calculated. Following our previous work, we calculate the short distance contributions under the factorization hypothesis, whereas the long distance contributions are modeled as the final state interactions, which are calculated with the one particle exchange model. We find that the decays' branching ratios are obviously larger, as they receive contributions of more polarization states. Among the decays that we investigate, the following have the largest branching fractions: estimated with fs; and with fs; and , , and with fs. By comparing the decay widths of pure color commensurate channels with those of pure bow-tie ones, we find that the bow-tie mechanism plays an important role in charm decays.

Discrete supertetrahedral clusters of metal chalcogenides are rare because of the difficulty involved in meeting global charge matching between the negative charge of the skeleton and counterion. We present herein the third type of a discrete chalcogenide cluster with a double T3 structure in the compound (HDBN)6[In20S33(DBN)6] (DBN = 1,5-diazabicyclo [4.3.0]-5-nonene), the anion of which features quasi-D3 symmetrical double-T3 In20S33 supertetrahedra with six cornered indium atoms coordinated by DBN molecules. DFT theory calculations of the interaction between host and guest show that this compound may have high kinetic stability and low photoelectric reactivity.

Metal-organic frameworks (MOFs) with excellent proton conducting ability are crucial to fuel cells, chemical sensors, and redox flow batteries, but achieving them remain a challenge because of the difficulty in simultaneous fulfillment of large number of proton carriers, high mobility of protons, and long-term durable proton conduction. To explore a simple, efficient, and general route toward highly proton-conducting MOFs, we propose herein an aliovalent substitution metal strategy for isostructural aminium-templated MOFs which benefit the acquisition of rich proton sources without modifying ligands or exchanging protic organic molecules. This idea is verified by 100-fold enhancement of conductivity in compounds (Me2NH2)2[Cd(mdhbqdc)2] (Cd-BQ) and (Me2NH2) (Me2NH)[In(mdhbqdc)2] (In-BQ) (H2mdhbqdc = dimethyl 3,6-dihydroxy-2,5-benzoquinone-1,4-dicarboxylic acid) that feature three-dimensional diamond-like structures with two-dimensional intersected channels. Accompanied by the in situ formation of an anilicate ligand, a great number of -OH groups are grafted onto the inner wall of pores, which interact with neutral Me2NH and/or protonated Me2NH2+ cations via N-H···O hydrogen bonds. The high concentration of protons and dynamics of protic amines in the porous framework readily leads to a moderate conductivity of In-BQ (2.10 × 10-4 S cm-1, at 303 K under 95% RH) and an activation energy of 0.73 eV (95% RH). It should be noted that the aliovalent substitution of Cd(II) for In(III) results in the doubling of dimethylaminium proton carriers in Cd-BQ, indicating more frequent hopping and multiple proton-transfer pathways. This indication is supported by a very high protonic conductivity of 2.30 × 10-2 S cm-1 and a reduced activation energy of 0.48 eV under the same conditions. Molecular dynamics simulations visually elucidate the fact that compared with In-BQ, aliovalent-substituted Cd-BQ has shorter proton-migration distances, which in combination with more proton numbers results in more frequent hopping and sliding of protons, in agreement with the experimental results.

Stimuli-responsive solid-state crystal dynamics or flexibility in metal–organic frameworks (MOFs) showing multiple structure changes is an arising interest for understanding the structure–property relationship and designing functional materials. In this article, dehydration-induced stepwise single-crystal to single-crystal (SC–SC) transformations are observed in two-dimensional 63-topological coordination polymer [Co(H2L)(H2O)2]·H2O (1), where H4L is 3,5-bis(3′,5′-dicarboxylphenyl)-1H-1,2,4-triazole. Upon thermal dehydration at 130 °C for 2 h, half lattice water in 1 can be released to form [Co(H2L)(H2O)2]·0.5H2O (2). By increasing dehydration temperature to 150 °C for 3 h, the third phase [Co(H2L)(H2O)2] (3) that is free of lattice water molecule is gained. Further increasing the dehydration temperature to 160 °C for 6 h, one of coordination water molecule can be released, giving rise to dicobalt-based 2D (3,6)-connected kgd double layer [Co(H2L)(H2O)] (4). During stepwise dehydration SC–SC transformatio...

Background China has a large volume of inter-provincial migrants, accounting for more than 11% of the total population. The economic benefits of inter-provincial migration have been well studied, whereas the health impacts related to environmental factors are generally ignored. Methods In this study, we use 1% national population sampling survey data from 2015 and daily PM2.5 (particles ≤ 2.5 µm in aerodynamic diameter) concentration data from 360 cities to analyze the health benefits associated with air pollution due to inter-provincial migration. The exposure-response function was used to estimate the economic value of these health benefits via the adjusted-human-capital and cost-of-illness methods. Results Considering a full-exposure scenario, inter-provincial migration resulted in a reduction in the PM2.5 exposure concentration of 3.94 µg/m3 in 2015, corresponding to a reduction of 6114 premature deaths, 233.4 thousand hospitalization cases, and 1.5 million asthma attacks. The corresponding economic value of these health benefits was about 10.44 billion yuan (0.02% of the national GDP in 2015). A protection scenario, assuming that the migrants protected themselves from air pollution, showed very similar results to the full-exposure scenario (PM2.5 exposure reduced by 3.60 µg/m3); hence, personal protection does not reduce significantly the health risks of air pollution. Conclusions At the national level, the labor force obtains both economic and health benefits. However, a high number of migrants flow out of the central region of China result in a labor deficiency and social imbalance. Migration to large cities provides economic benefits at the expense of health. Environmental migration becomes an increasingly important motivation for inter-provincial migration, which places new pressure on policy makers to consider social welfare and environmental protection in the provinces.

Reactions of CuCl2, K2[Ni(CN)4]/K3[Co(CN)6], and 5-amino-1H-tetrazole led to cyanide-bridged mixed-valence Cu(II/I) complexes, [Cu(H2O)3Cu3(CN)5] (1) and [Cu(H2O)4][Cu4(CN)6] (2).The uncommon semi-closed {Cu2(CN)3} dimmers in 1 are bridged by μ3-C,C,N cyanide ligands to afford rare 1D centipedal-like chain motifs, which are further bridged by μ2-C,N and metalloligand “CN–Cu(4)–CN” to finish sophisticated zeolite-like 3-D structure. Topologically, 1 is the first example of uninodal 7-connected sev-like cyanide-bridged network. Compound 2 consists of two-dimensional honeycomb-related anionic layers [Cu4(CN)6]2 −, within which the [Cu(H2O)4]2 + cations are intercalated into alternate interlamellar space. Compound 1 shows antiferromagnetic couple arising from pure ground-state configuration of Cu(II) mediated by diamagnetic bridges –CN–CuI–CN −. The inclusion compound 2 shows blue photoluminescence originated from Cu(I) center to the unoccupied π* orbital of the cyanide ligand (MLCT) charge transfer.

China faces the dual challenge of mitigating climate change and preventing air pollution. The coordinated control of both problems has become an issue of widespread concern. This study combined environmentally extended input-output analysis and structural path analysis to analyze the CO2, SO2, NOx, black carbon, and PM2.5 emissions embodied in the production supply chain of China in 2012. The results showed that electricity and heat production, nonmetallic mineral products along with the smelting and pressing of metal were primary sources of environmental emissions from the production perspective, and construction contributed 20–38% relevant emissions from the consumption perspective. Among the 100 largest paths, 22 common critical paths accounted for 16–37% of relevant emissions, meaning that measures focusing on these shared paths will have obvious co-controlling effects. These 22 critical supply chains were mainly driven by fixed capital formation and exports. The dominant sectors included the construction, electricity and heat production, transportation and storage, and construction-materials production (nonmetallic mineral products, smelting and pressing of metal). Therefore, measures from the production-side and the consumption-side should be given equal attention to effectively co-control such emissions. Measures to decrease energy intensity, thus reducing end-of-pipe discharge in these sectors, rather than to remove specific pollutants, represent the most promising production-related measures. Moreover, slowing construction growth by guiding investments and encouraging the use or export of products with lower emissions using environmental information labels are essential consumption-related policies.

Solvothermal reactions of metal salts, 3-amino-1,2,4-triazole-5-carboxylic acid (H2atzc) and ammonium oxalate in different temperature produced two metal azolate frameworks, namely, [Cu3(atzc)2(atz)(ox)]·1.5H2O (1) and [Co5(atz)4(ox)3(HCOO)2]·DMF (2) (H2atzc=3-amino-1,2,4-triazole-5-carboxylic acid, Hatz=3-amino-1,2,4-triazole, and ox=oxalate), in which the atzc precusor was in situ decarboxylated. Structural determination reveals that 1 contains [Cu3(atzc)2(atz)]2− layers of mixed μ4-atzc and μ3-atz ligands, which are pillared by ox2− groups to form a 3D porous framework. Compound 2 contains 2D layers with basic spindle-shaped decanuclear units, which extended by ox2− and formates to form 3D porous framework. Gas adsorption investigation revealed that two kinds of frameworks exhibited selective CO2 over N2 sorption. Moreover, activated 2 shows H2 storage capacity. Additionally, magnetic properties of both the compounds have been investigated.

Although a variety of functional metal-organic frameworks (MOFs) have been synthesized, post-modified, and applied in various areas, there is little knowledge about how molecular cluster building units are stepwise evolved into MOFs via intermediates. Coordination bonds are generally stronger than hydrogen bonds, and thus equivalent replacement of X-H···Y hydrogen bonds by X-M-Y coordination bonds can transform hydrogen bond networks into MOFs. In this work, solvothermal in situ reduction reactions of CuBr2 and 1,4-diazoniabicyclo[2,2,2]octane (DABCO) generated a myriad of tunable photoluminescent cuprous body-centered cubic bromide cluster-based networks with the general formula [Cu4+xH4-xBr6(DABCO)4](HCO2)2·S (x = 0, 0.56, 0.81, 1.27, 1.39, 2.56, 2.78, and 4 for compounds 1-8, respectively). All of these compounds crystallize in the cubic space group with the largest volume difference being only 5.2%, but they belong to three remarkably different kinds of crystals. Complex 1 is a molecular crystal and consists of tetrahedral [Cu4Br6(HDABCO)4](2+) clusters with monodentate HDABCO groups that are supported via N-H···Br synthons in the hydrogen bond network. Compound 8 is a [Cu8Br6](2+) cube cluster-based MOF with bridged DABCO ligands. Complexes 2-7 are seemingly impossible Cu/H-substituted solid solutions of 1 and 8. The CuBr framework components in 1-8 are Cu4Br6, Cu4.56Br6, Cu4.81Br6, Cu5.27Br6, Cu5.39Br6, Cu6.56Br6, Cu6.78Br6, and Cu8Br6, respectively. Crystallization kinetics studies revealed that the [Cu4Br6(HDABCO)4](2+) cluster-based hydrogen bond network (1) was initially formed such that N-H···Br hydrogen bonds could be stepwise replaced by N-Cu-Br coordination bonds to form the [Cu8Br6](2+) cube cluster-based MOF (8) via solid solutions. These observations directly reveal the equivalence and transformation between the N-H···Br hydrogen bond and the N-Cu-Br coordination bond and the evolutionary mechanism of a molecular crystal to a MOF via solid solutions, which is of fundamental importance in materials but has never before been revealed. DFT calculations suggest that equivalent replacement of a N-H···Br hydrogen bond by a N-Cu-Br coordination bond is exothermic and exergonic, which also supports the transformation from molecule 1 to MOF 8.

Five new polyoxometalate-based metal organic frameworks, [Cu4(ppz)4(PO4)]·[CuBr2] (1), [Cu4(ppz)4(MoO4)2(H2O)]·2H2O (2), [Cu(Hppz)(Mo2O7)] (3), [Cu2(ppz)2(Mo3O10)] (4), and [Cu6(ppz)6(PMo3VMo9VIO40)] (5) (Hppz = 2-(1H-pyrazol-3-yl)pyrazine), have been hydrothermally synthesized and fully characterized, in which a planar Cu2(ppz)2 dimer acts as a secondary building unit (SBU) and provides up to six potential binding sites. In virtue of the strong Jahn–Teller (JT) effect of Cu(II) ions, the potential binding sites in the Cu2(ppz)2 SBU can facilely be occupied by auxiliary oxygen-donor anions and/or outward pyrazine nitrogen atoms of neighboring SBUs. The auxiliary oxygen-donor anions in compounds 1–5 range from simple phosphate and molybdate, zonal Mo2O72– and Mo3O102– to a spherical three-electron reduced Keggin anion [PMo12O40]6–, respectively. Compound 1 contains an unprecedented 3D (4,6)-connected cationic open framework [Cu4(ppz)4(PO4)]+ with 1D channels filled by linear CuBr2– anions, where the Cu2(pp...

Solvothermal treatment of a mixture of Se, SnC12, CoC12, and dien (dien = diethylenetriamine) generated yellow crystals of [Co(dien)2]2Sn2Se6 (1), which could transform into black 2 with the same formula via rinsing with water. In the presence of water, ultrasound irradiation of black 2 went back to yellow 1. The reversible ultrasound and solvent-induced chromism has never been observed before. Compared with yellow 1, hyperchromism was apparent around 550 nm in the visible absorption spectrum of 2. The fluorescent properties for 1 and 2 were investigated and the mechanisms were validated by density functional theory calculations on the experimental geometries. In addition, electron paramagnetic resonance spectra of yellow 1 are similar to chromic black 2 in the signal at g = 4.22 and g = 2.19; the signal at g = 2.19 of 2 shows a sharp increase.

Two cuprous iodide polymorphs formulated as [N(CH3)4][Cu2I3] α and β were synthesized, in which N(CH3)4+ template that never existed in the reaction materials are in situ generated via cleavage of C N bonds and N-alkylation reactions. Solvothermal reaction of copper source, hexamethylenetetramine and HI in methanol solution at 150 °C led to α and β polymorphs. Two polymorphs have been synthesized via subtle modification of the experimental condition, which indicates that the small force is also sufficient for energy difference for polymorphs. α polymorph contains one-dimensional Cu2I3− chain in which the copper atoms are arranged into a zigzag lattice; β polymorph is composed of novel ladder-like chains which can be considered as being built up by Cu12I18 and Cu2I3 two types of secondary building units. The UV–vis absorption spectra for α and β polymorphs were investigated in reflectance mode in the solid state at room temperature, exhibiting that they belong to potential semiconductors. The excitation and emission in α and β are very distinct, which highlight that the molecular packing in polymorphs is critical to photophysical properties.

Four novel coordination polymers based on asymmetric triangular 5-(4′-carboxylphenyl) nicotinic acid (H2cpna), namely, Ni(cpna)(H2O)2 (1), M2(cpna)2(H2O)3·0.5H2O·DMF [M = Ni for (2), Co for (3)] and Ni3(Hcpna)2(cpna)2(H2O)4·2H2O (4), have been synthesized under solvothermal conditions. All of the four compounds contain low nuclear metal clusters as secondary building units (SBUs). Complex 1 exhibits two-dimensional (3,6)-connected (43)2(46.66.83)-kgd topology, in which cpna ligands and edge-shared dinuclear SBUs act as 3-connected and 6-connected nodes, respectively. Compounds 2 and 3 are constructed by corner-shared dinuclear SBUs and show an unprecedented (3,6)-connected chiral (42.6)2(44.62.88.10)-anh (flu-3, P6222) topology. In 4, linear trimers are ligated by six cpna ligands to form a planar (43)2(46.66.83)-kgd layer, and adjacent layers are further linked by Hcpna– ligands through Ni–O and Ni–N bonds to form three-dimensional (3,8)-connected (43)2(46.618.84)-tfz-d net. Both 1 and 4 crystallize in t...

Reactions of CuCl2, K3[Fe(CN)6]/K4[Fe(CN)6], and pyrazine (pyz) in water solution at 160 °C/170 °C for 6 days led to two luminescent supramolecular isomers with stoichiometry [Cu2(pyz)(CN)2]·[CuCN] (1 and 2), which show 3D pseudopolyrotaxane structures with 1D [Cu(CN)]∞ chains penetrating 2D [Cu2(pyz)(CN)2] sheets. Isomer 1 contains linear, trigonal, and tetrahedral Cu(I) atoms, which are linked by pyz and cyanide groups into unprecedented (3,4)-connected Shubnikov-type (5,34) sheets, and these sheets are penetrated by [Cu(CN)]∞ chains via unsupported CuI–CuI interactions. In contrast, the [Cu2(pyz)(CN)2] sheets in isomer 2 can be viewed as a classical (6,3)-topological brick wall layer, which are also penetrated by [Cu(CN)]∞ chains in the absence of cuprophilicity. Schematically, the brick wall and Shubnikov-type (5,34) nets can be formed via arrangement of brick rows in ABAB and ABBA modes, respectively. It is worth noting that cyanide sources played a crucial role in the formation of supramolecular iso...

By using environmental friendly K3[Fe(CN)6] as a cyanide source, hydrothermal reactions of CuCl2 and diamines resulted in four Cu2(1,1,2-μ3-CN)2(CN)4 dimer-based organic templated cuprous cyanide open frameworks, namely, [H1.5mepip]2[Cu4(CN)7] (1), [H1.5etpip]2[Cu4(CN)7] (2), [H2me2pip][Cu3(CN)5] (3), and [H2dmpa][Cu4(CN)6] (4) (mepip = N-methylpiperazine; etpip = N-ethylpiperazine, me2pip = N,N-dimethylpiperazine, dmpa = 3-dimethyl-aminopropylamine). Isomorphic 1 and 2 show three-dimensional (3-D) (4,6)-connected FeS2-like open frameworks constructed by 4-connected Cu(CN)4 monomers and 6-connected Cu2(CN)6 dimers. Complex 3 shows an unprecedented 3-D (4,6)-connected open framework in which the ratio of 4-connected Cu(CN)4 monomers to 6-connected Cu2(CN)6 dimers is 1:1. Complex 4 shows a 3-D (3,6)-connected AgIn2-like open framework constructed by 3-connected Cu(CN)3 monomers and 6-connected Cu2(CN)6 dimers. Different from CuCN/amine coordination polymers, the protonated organic diamines in 1–4 act as tem...

Hydrothermal reaction of copper(II) chloride with 2-hydroxypyrimidine generated double salt of [Cu2Cl(μ4-pymo)] (1) (Hpymo = hydroxylpyrimidine) while hydrothermal treatment of CuCl2, NaN3 and acetonitrile resulted in double salt of [Cu2(mtta)Cl] (2) (Hmtta = 5-methyltetrazole) in which in situ [2 + 3] cycloaddition reactions of acetonitrile with azide formed mtta ligand. X-ray single crystal structural analyses revealed that 1 shows a two-dimensional layer formed by fusion of one-dimensional [ Cu 2 ( opym ) ] n n + and [ Cu 2 Cl ] n n + structural motifs. The two-dimensional layers in 1 are held together by C–H⋯Cl hydrogen bonds to form three-dimensional supramolecular array. Compound 2 has a three-dimensional framework constructed from [ Cu 2 ( mtta ) ] n n + ribbons and [Cu8Cl4]4+ units. Uncommon coordination modes of μ4-1,2κO:3κN:4κN′ pymo and μ4-Cl (Cl at the apex of a Cu4Cl square pyramid) in 1 and μ4-η1:η1:η1:η1 mtta in 2 were also observed. The short Cu(I)⋯Cu(I) distances were found in 1 and 2, indicating the existence of Cu(I)⋯Cu(I) interactions.

Two isostructural mixed-valence vanadium phosphonoacetates H2(DABCO)[VIVO(H2O)VIII(OH)(O3PCH2CO2)2]·2.5H2O (1) and H2(PIP)[VIVO(H2O)VIII(OH)(O3PCH2CO2)2]·2.5H2O (2) have been synthesized. They crystallize in the orthorhombic space group Pnna with a = 7.0479(10) A, b = 15.307(2) A, and c = 17.537(3) A for 1 and a = 7.0465(9) A, b = 15.646(2) A, and c = 17.396(2) A for 2. X-ray single-crystal diffraction reveals that 1 and 2 have a three-dimensional open framework featuring 16-ring ellipsoid channels that are filled with doubly protonated 1,4-diazabicyclo[2,2,2]octanium/piperazinium cations and water molecules. According to the classification in metal−organic frameworks, 1 and 2 contain infinite (−O−V−)∞ chains that are cross-linked by “metalloligand” [VO(H2O)(O3PCH2CO2)2]4- into a 3-D net of the sra topology. The temperature dependence of the magnetic susceptibility of 1 shows that the χmT value in the range of 60−320 K is constant of 1.105 cm3 K mol-1/V2 unit, and upon further cooling, the χmT value rapid...

Hydrothermal reaction of CuBr2, 4,4′-bipyridine and ethanol/methanol generated two copper (I) bromide complexes with in situ alkylated 4,4′-bipyridium, namely [C14H18N2][Cu5Br7] (1) and [C12H14N2][Cu4Br6] (2). The structure of 1 consists of Cu 5 Br 7 2 - chains and N,N′-diethyl-4,4′-bipyridinium. The underlying structural motif in Cu 5 Br 7 2 - of 1 is the Cu5Br capped square pyramid, which is different from the Cu5Br2 pentagonal bipyramidal structural motif in various documented Cu 5 Br 7 2 - anions. The Cu 5 Br 7 2 - in 1 contains untypical μ5-bromide, with which five copper atoms forms a capped square pyramid rather than a pentagonal pyramid as predicted by Subramanian and Hoffmann. Compound 2 is isostructural with [C12H14N2][Cu4Cl6] reported by Willett, and consists of Cu 4 Br 6 2 - chains and N,N′-dimethyl-4,4′-bipyridinium. The Cu 4 Br 6 2 - chain is composed of alternating Cu6Br6 and Cu2Br6 units.

Seven new metal phosphonoacetates, namely, [Zn7(OH)2(ppat)4(H2O)2] (1), H3O[Zn(ppat)] (2), [Zn3(4,4‘-bpy)(ppat)2] (3), H2dmpz0.5[Zn(ppat)]·H2O (4), (H3O)2[Co3(OH)2(ppat)2] (5), H24,4‘-bpy[VIV2O2(ppat)2] (6), and [FeIII(ppat)(H2O)] (7) (H3ppat = phosphonoacetic acid, 4,4‘-bpy = 4,4‘-bipyridine, dmpz = N,N‘-dimethylpiperazine) were hydrothermally synthesized by the in situ hydrolysis of triethyl phosphonoacetate route. X-ray crystallography reveals that 1 shows a two-dimensional layered structure containing octahedral, tetrahedral, and trigonal bipyramidal Zn sites and an unprecedented inorganic Zn−O ribbon; 2 has a three-dimensional framework with one-dimensional dumbbell-shaped channels encapsulating protonated water molecules; 3 is a neutral three-dimensional framework constructed by [Zn(4,4‘-bpy)]n2n+ chains and [Zn(ppat)]nn- layers, two types of structural motifs; 4 shows a three-dimensional hydrogen bond network constructed by [Zn(ppat)]- anionic layers and N,N‘-dimethylpiperazinium cations; 5 is a la...

Colorless needle-like crystals of α-(NMe4)[Cu2I3] are prepared by solvothermal reaction of CuI, hexamethylenetetramine, and HI in MeOH in a molar ratio of 5:2:7:150 (autoclave, 150 °C, 120 h; 61% yield).

The first coordination polymer of 2,2′-oxydisuccinate, [Cd2(meso-odsc)(H2O)] (odsc = meso-2,2′-oxydisuccinate), was hydrothermally synthesized from CdSO4 and D,L-malic acid; X-ray crystallography shows that the D,L-malic acid was transformed in situ into meso-odsc via intermolecular dehydration coupling.

To optimize the preparation of ampelopsin from Ampelopsis Cantoniensis Planch.The extraction and purification process was studied by the uniform design with the extract of ampelopsin content and purity as markers. The facters which influence the extraction and the purification of ampelopsin content were studied by uniform design.The optimum extraction and purification process: the concentration for alcohol was 90%, and refluxing quartic, 1.5 h each time; extraction by petroleum ether quintic, the mount of active carbon was 1 g/100 g of the medicine material, and recrystaling thrice.This extraction process has higher yield of ampelopsin and is available for production.

In the title compound, [Fe(C6H12NO5)2], the FeIIion lies on an inversion center and is coordinated by two N atoms and four O atoms from two tridentateN-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]glycine ligands, forming a slightly distorted octahedral coordination environment. In the crystal, O—H...O, O—H...N and weak C—H...O hydrogen bonds link molecules, forming a three-dimensional network.

Five new cuprous halides formulated as [etpy][Cu(3)I(4)] 1, [mepy][Cu(2)Br(3)] 2, [mepy][Cu(2)I(3)] 3 [dmebpp][Cu(7)Br(9)] 4 and [dmeDABCO](4)[Cu(8)I(16)] 5 (etpy = N-ethylpyridyl; mepy = N-methylpyridyl; dmebpp = N,N'-dimethyl-1,3-bis(4-pyridyl)propane; dmeDABCO = N,N'-dimethyl-1,4-diazabicyclo-[2.2.2]octane) have been prepared by solvothermal reactions of a copper source, halides and N-heterocyclic ligands in alcoholic solution. 1 contains an unprecedented trigonal two-dimensional cuprous halide layer Cu(3)I(4)(-) constructed from trimeric Cu(3)I(8) units via sharing peripheral mu(3)-iodines; isostructural 2 and 3 contain infinite Cu(2)X(3)(-) chains in which the copper atoms are arranged into a ladder; 4 is composed of novel twofold helical cuprous halide chains Cu(7)Br(9)(2-) built up by CuBr(4) and CuBr(3); 5 contains an infinite edge-sharing tetrahedral chain with a periodic sequence of eight CuI(4) tetrahedra. In situ alkylation reactions of N-heterocycles with alcohols generated organic cationic templates, which played an important role in the control of the structures of anionic cuprous halides. A possible alkylation mechanism of N-heterocycles in the system has been proposed. The fluorescence properties of 1 and 4 were investigated. Time-dependent density functional theory (TD-DFT) calculations were carried out on the excited electronic states 1 of in order to understand the emission mechanism.