An Efficient, One-Pot Transamidation of 8-Aminoquinoline Amides Activated by Tertiary-Butyloxycarbonyl.

The efficient, one-pot access to the transamidation of 8-aminoquinoline (8-AQ), notorious for its harsh removal conditions, has been widely employed as an auxiliary in C⁻H functionalization reactions due to its strong directing ability. In this study, the facile and mild Boc protection of the corresponding 8-AQ amide was critical to activate the amide C(acyl)⁻N bond by twisting its geometry to lower the amidic resonance energy. Both aryl and alkyl amines proceeded transamidation in one-pot, user-friendly conditions with excellent yields.

Highly Stable Mesoporous Zirconium Porphyrinic Frameworks with Distinct Flexibility.

The construction of highly stable metal-porphyrinic frameworks (MPFs) is appealing as these materials offer great opportunities for applications in artificial light-harvesting systems, gas storage, heterogeneous catalysis, etc. Herein, we report the synthesis of a novel mesoporous metal-porphyrinic framework (denoted as NUPF-1) and its catalytic properties. NUPF-1 is constructed from a new porphyrin linker and a Zr6 O8 structural building unit, possessing an unprecedented doubly interpenetrating scu net. The structure exhibits not only remarkable chemical and thermal stabilities, but also a distinct structural flexibility, which is seldom seen in metal-organic framework (MOF) materials. By the merit of high chemical stability, NUPF-1 could be easily post-metallized with [Ru3 (CO)12 ], and the resulting {NUPF-1-RuCO} is catalytically active as a heterogeneous catalyst for intermolecular C(sp(3) )-H amination. Excellent yields and good recyclability for amination of small substrates with various organic azides have been achieved.

Direct oxidative amidation of aldehydes with amines catalyzed by heteropolyanion-based ionic liquids under solvent-free conditions via a dual-catalysis process.

A simple and efficient procedure for the synthesis of amides directly from aldehydes and amines catalyzed by heteropolyanion-based ionic liquids under solvent-free conditions has been reported. The practical protocol was found to tolerate a wide range of substrates with different functional groups. Moderate to excellent yields, solvent-free media, and operational simplicity are the main highlights. The proposed dual-catalysis mechanistic pathway was briefly investigated. Furthermore, the heteropolyanion-based ionic liquids were easily reusable for this oxidative amidation.

A Convenient Strategy for Designing a Soft Nanospace: An Atomic Exchange in a Ligand with Isostructural Frameworks.

Direct observation of gas molecules confined in the nanospace of porous materials by single-crystal X-ray diffraction (SXRD) technique is significant because it leads to deep insight into the adsorption mechanism and the actual state of the adsorbents in molecular level. A recent study revealed that flexibility is one of the important factors to achieve periodic guest accommodation in the nanospace enabling direct observation of gas molecules. Here, we report a convenient strategy to tune the framework flexibility by just an atomic exchange in a ligand, which enables us to easily construct a soft nanospace as the best platform to study gas adsorption. Indeed, we succeeded to observe C2H2 and CO2 molecules confined in the pores of a flexible porous coordination polymer (PCP-N) in different configurations using SXRD measurement, whereas gas molecules in a rigid framework (PCP-C) isostructural to PCP-N were not seen crystallographically. The result of the coincident in situ powder X-ray diffraction and adsorption measurement for PCP-N unambiguously showed that the framework could flexibly transform to trap gas molecules with a commensurate fashion. In addition, for PCP-N, we found that the adsorbed gas molecules induced significant structural change involving dimensional change of the pore from one-dimensional to three-dimensional, and subsequently, additional gas molecules formed periodic molecular clusters in the nanospace.

Copper catalyzed C-O bond formation via oxidative cross-coupling reaction of aldehydes and ethers.

A practical and efficient construction of C-O bonds via oxidative cross-coupling reaction of aldehydes and ethers has been realized under open air. When 2 mol% copper was used as the catalyst, various α-acyloxy ethers were obtained with up to 93% isolated yield.

Binding of a coordinatively unsaturated mercury(II) thiolate compound by carboxylate anions.

Reactions of [Hg(Tab)2](PF6)2 (TabH = 4-(trimethylammonio)benzenethiol) (1) with acetic acid (HAc), propanoic acid (HPro), salicylic acid (HSal), benzoic acid (HBez), malonic acid (H2Mal), oxalic acid (H2Oxa), adipic acid (H2Adi), or methylimindiacetic acid (H2Meida) in the presence of Et3N gave rise to a family of mercury(II)-thiolate-carboxylate compounds, [Hg(Tab)2(Ac)](PF6) · 0.5H2O (2 · 0.5H2O), [Hg(Tab)2(Pro)](PF6) (3), [Hg(Tab)2(Sal)](PF6) · MeOH (4 · MeOH), [Hg(Tab)2(Sal)](Sal) · MeOH (5 · MeOH), [Hg(Tab)2(Bez)](PF6) · H2O (6 · H2O), [Hg(Tab)2(HMal)](Mal)0.5 H2O (7 · H2O), [{Hg(Tab)2}2(µ-Oxa)](PF6)2 H2O (8·2H2O), [{Hg(Tab)2}2(µ-Adi)](PF6)2 (9), [Hg(µ-Tab)(µ-Adi)]2n (10), and [Hg(Tab)2(Meida)] · 2.5H2O (11 · 2.5H2O). These compounds were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H NMR, and single-crystal X-ray crystallography. Each mercury(II) atom in [Hg(Tab)2](2+) dication of 2-7 is further coordinated by two oxygen atoms from one Ac(-), Pro(-), Sal(-), Bez(-), Mal(2-) or HMal(-) anion, forming a unique seesaw-shaped coordination geometry. In 8 or 9, two [Hg(Tab)2](2+) dications are connected by one bridging oxalate or adipate dianion to generate a dimeric structure with each mercury(II) center adopting a seesaw-shaped geometry. In 10, a pair of octahedrally coordinated mercury(II) atoms are bridged by two sulfur atoms of two Tab ligands to form a [Hg(µ-Tab)2Hg](4+) fragment, which is further connected to its equivalent ones via four adipate dianions, thereby forming a rare two-dimensional network. In 11, the mercury(II) atom in the [Hg(Tab)2](2+) dication is coordinated by one nitrogen and two oxygen atoms from one Meida(2-) dianion to have a rare square pyramidal geometry. The formation of 2-11 from 1 may be applicable to mimicking the interactions of the mercury(II) sites of Hg-MerR and Hg-MT with various amino acids encountered in nature.

4-[2-(Hydrogen phosphonato)-2-hydroxy-2-phosphonoethyl]pyridinium.

The title compound, C(7)H(11)NO(7)P(2), exists as a zwitterion in which the positive charge resides on the protonated pyridyl N atom and the negative charge on one of the two phosphate groups. In the crystal, adjacent molcules are linked by O-H⋯O and N-H⋯O hydrogen bonds into a three-dimensional network.

Advances in Research on Genetic Relationships of Waterfowl Parvoviruses.

Derzsy's disease and Muscovy duck parvovirus disease have become common diseases in waterfowl culture in the world and their potential to cause harm has risen. The causative agents are goose parvovirus (GPV) and Muscovy duck parvovirus (MDPV), which can provoke similar clinical symptoms and high mortality and morbidity rates. In recent years, duck short beak and dwarfism syndrome has been prevalent in the Cherry Valley duck population in eastern China. It is characterised by the physical signs for which it is named. Although the mortality rate is low, it causes stunting and weight loss, which have caused serious economic losses to the waterfowl industry. The virus that causes this disease was named novel goose parvovirus (NGPV). This article summarises the latest research on the genetic relationships of the three parvoviruses, and reviews the aetiology, epidemiology, and necropsy characteristics in infected ducks, in order to facilitate further study.

Interactions of a cationic mercury(II) thiolate complex [Hg(Tab)2](PF6)2 with N-donor ligands.

Reactions of [Hg(Tab)(2)](PF(6))(2) (1) with phen, 2,2'-bipy, py, N-Meim, N-(i)Prim, en, eten, tmen, dap, and dpt gave rise to a family of cationic mercury(II) thiolate complexes, [Hg(Tab)(2)(L)](PF(6))(2).S (2, L = phen, S = 2MeOH; 3, L = 2,2'-bipy, S = DMF), [Hg(Tab)(2)(L)(2)](PF(6))(2) (4, L = py; 5, L = N-Meim), [Hg(Tab)(2)(N-(i)Prim)](PF(6))(2) (6), [Hg(Tab)(2)(L)](PF(6))(2).0.5MeCN (7, L = en; 8, L = eten), and [Hg(Tab)(2)(L)](PF(6))(2) (9, L = tmen; 10, L = dap; 11, L = dpt). These complexes were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H NMR, and single-crystal X-ray crystallography. The Hg atom in [Hg(Tab)(2)](2+) dications of 2-5 is further coordinated either by two N atoms from one phen or 2,2'-bipy ligand or by two N atoms from two py or N-Meim ligands, affording a distorted seesaw-shaped coordination geometry. In 6, the Hg atom of the [Hg(Tab)(2)](2+) dication is coordinated by one N atom of the N-(i)Prim ligand, forming a T-shaped coordination geometry, and these [Hg(Tab)(2)(N-(i)Prim)](2+) dications are further coordinated to another S atom of Tab from the adjacent unit, giving a chain structure. The Hg atoms in [Hg(Tab)(2)](2+) dications of 7-11 are chelated by two N atoms from one diamine molecule such as en in 7, eten in 8, tmen in 9, or dap in 10 or by two N atoms from the triamine molecule dpt in 11, forming a distorted seesaw-shaped coordination geometry. In all of these structures, the original trans configuration of the [Hg(Tab)(2)](2+) dication of 1 is changed via rotation and/or switching of the two Tab species along the S-Hg-S line together with the rotation of the phenyl groups of the Tab ligands. The results may provide interesting insight into mimicking of the interactions of the Hg(Cys)(2) linear species in Hg-MerR and Hg-MT with various N-donor ligands encountered in nature and its potential changes in the structural chemistry (bond length, angles, configurations, etc.).

Charge, adsorption, water stability and bandgap tuning of an anionic Cd(ii) porphyrinic metal-organic framework.

Due to the designability of metal-organic frameworks (MOFs), semiconductor MOFs have become the focus of research as photocatalysts of useful chemical processes utilizing clean solar energy. In this work, we developed a method of tuning the framework charge of MOF materials and determined how the framework charge can affect the band edge positions and bandgaps of the novel anionic Cd(ii) porphyrinic metal-organic framework (PMOF) 1 ([Cd3.2(H2TCPP)2][(CH3)2NH2]1.6). It was constructed from H2TCPP4- (H6TCPP = tetrakis(4-carboxyphenyl)-porphyrin) and Cd(ii), forming a tube-like structure, and shown to have a negatively charged framework with a 60% occupancy of one type of Cd(ii) ion. By increasing the reaction time and the amount of Cd(ii) ions in the reactants, the nearly neutral counterpart of PMOF 1 was also obtained. The [(CH3)2NH2]+ counterions of PMOF 1 were also exchanged with Li+. Although the surface area of PMOF 1 and its derived PMOFs were only 407-672 m2 g-1, the CO2 and CH4 uptakes reached, respectively, 44-65 ml g-1 (8.7-12.7%) and 22-26 ml g-1 (1.6-1.8%) each at 1.0 atom and 273 K; at 9.0 atm these values nearly tripled. Li+-exchanged 1 favoured N2, CO2 and CH4 adsorption, especially at 9 atm and a relatively low temperature (273 K). PMOF 1 subjected to a solvent exchange process showed an unstable structure in water, while PMOF 1 not subjected to this process was found to be stable in water. Thus, a method for making water-stable divalent-metal carboxylate MOFs was proposed. The counter ion type showed little effect on the band-edge positions and bandgaps, but the framework charge did show effects. Under visible light and with tris(2,2'-bipyridine)dichlororuthenium(ii) (Ru(bpy)3Cl2) as the co-catalyst and triethylamine (TEA) as the sacrificial agent, the efficiency of CO production resulting from CO2 reduction using 1-DMF reached 56 µmol g-1 h-1, about 5 times greater than that for the system without using Ru(bpy)3Cl2.

Bis(5-aminotetrazole-1-acetato-kappaO)tetraaquacobalt(II) and catena-poly[[cadmium(II)]-bis(mu-5-aminotetrazole-1-acetato-kappa3N4:O,O')].

The Co(II) atom in bis(5-aminotetrazole-1-acetato)tetraaquacobalt(II), [Co(C3H4N5O2)2(H2O)4], (I), is octahedrally coordinated by six O atoms from two 5-aminotetrazole-1-acetate (atza) ligands and four water molecules. The molecule has a crystallographic centre of symmetry located at the Co(II) atom. The molecules of (I) are interlinked by hydrogen-bond interactions, forming a two-dimensional supramolecular network structure in the ac plane. The Cd(II) atom in catena-poly[[cadmium(II)]-bis(mu-5-aminotetrazole-1-acetato], [Cd(C3H4N5O2)2]n, (II), lies on a twofold axis and is coordinated by two N atoms and four O atoms from four atza ligands to form a distorted octahedral coordination environment. The Cd(II) centres are connected through tridentate atza bridging ligands to form a two-dimensional layered structure extending along the ab plane, which is further linked into a three-dimensional structure through hydrogen-bond interactions.

Synthesis and properties of a novel quarternerized imidazolium [α-PW12O40]3- salt as a recoverable photo-polymerization catalyst.

A recoverable photo-polymerization catalyst based on an imidazolium and a polyoxometalate, viz., (BMIm)2(DMIm)PW12O40 (where, BMIm = 1-butyl-3-methylimidazolium, DMIm = 3,3'-dimethyl-1,1'-diimidazolium) is reported. It catalyzes photo-polymerization of several industrially important monomers like styrene, methyl methacrylate, butyl methacrylate and vinyl acetate. The catalyst is recoverable and hence can be reused. The molecular weight and polydispersity index can be controlled reasonably and a reaction pathway is proposed. The synthesis of this novel catalyst is reported and the catalyst has been characterized using standard techniques such as single crystal X-ray diffraction studies, cyclic voltammetry and various spectroscopic methods such as Fourier transform infrared spectroscopy, (1)H NMR spectroscopy, EPR spectroscopy and UV-Vis spectroscopy. DFT calculations have been used to explain the catalyst's photo-chemical activity.

Zinc and cadmium 2-pyrazinephosphonates: syntheses, structures and luminescent properties.

Three new metal(II) 2-pyrazinephosphonates have been synthesized by hydrothermal reactions based on 2-pyrazinephosphonic acid (C(4)H(3)N(2)PO(3)H(2)1) as ligand, namely, Zn(C(4)H(3)N(2)PO(3)) (2), Cd[(C(4)H(3)N(2)PO(3))(H(2)O)] (3) and Cd[(C(4)H(3)N(2)PO(3)H)Cl]·H(2)O (4). In compound 2, the O-P-O bridged inorganic layers are pillared by pyrazinyl groups into a three-dimensional network. In compound 3, the {CdO(5)N} and {CPO(3)} polyhedra are interconnected via edge and corner-sharing into a metal phosphonate layer. In compound 4, the {Cd(2)Cl(2)} dimers are linked by O-P-O bridges into a one-dimensional double chain, and the chains are joined into a layer by pyrazinyl groups. Here we employ pyrazinephosphonic acids as structure directing motifs to form extended structures and materials with interesting luminescent properties. The luminescent properties studied have also been described.

Group 12 metal zwitterionic thiolate compounds: preparation and structural characterization.

Reactions of TabHPF(6) (Tab = 4-(trimethylammonio)benzenethiolate) with three equiv. of M(OAc)(2)·2H(2)O (M = Zn, Cd) gave rise to two tetranuclear adamantane-like compounds, [M(4)(µ-Tab)(6)(Tab)(4)](PF(6))(8)·S (·S: M = Zn, S = DMF·4H(2)O; ·S: M = Cd, S = DMF·5H(2)O). The similar reactions of MCl(2) (M = Zn, Cd, Hg) with four equiv. of TabHPF(6) in the presence of Et(3)N afforded three mononuclear compounds [M(Tab)(4)](PF(6))(2)·S (·S: M = Zn, S = 2(H(2)O)(0.5); ·S: M = Cd, S = 2(H(2)O)(0.5); ·S: M = Hg, S = 2DMF). Treatment of the precursor complex or with equimolar MCl(2) and two equiv. of TabHPF(6) and Et(3)N produced one dinuclear compounds [M(µ-Tab)(Tab)(2)](2)(PF(6))(4)·2DMF·2H(2)O (·2DMF·2H(2)O: M = Zn; ·2DMF·2H(2)O: M = Hg) while analogous reactions of with CdCl(2)·2H(2)O gave rise to [Cd(µ-Tab)(2)(Tab)](2)(PF(6))(4)·2DMF (·2DMF). These compounds were characterized by elemental analysis, IR spectra, UV-Vis spectra, (1)H NMR and single-crystal X-ray crystallography. In or , four M(2+) ions and six S atoms of Tab ligands constitute an adamantane-like [M(4)(µ-S)(6)] cage in which each M(2+) ion is tetrahedrally coordinated by one terminal S and three bridged S atoms from four different Tab ligands. In , each M(2+) center of the [M(Tab)(4)](2+) dication is tetrahedrally coordinated by four S atoms of Tab ligand. Two [M(Tab)(2)](2+) dications in or are further bridged by a pair of Tab ligands to form a dimeric [M(µ-Tab)(Tab)(2)](2)(4+) structure. Each dimeric [(Tab)Cd(µ-Tab)(2)Cd(Tab)](4+) unit in is linked to its two neighboring units via two couples of bridging Tab ligands, thereby generating a unique 1D cationic chain. These results may provide useful information on interpreting structural data of MTs containing group 12 metals.

Synthesis and structural and magnetic characterization of a hexadecanuclear cobalt phosphonate compound.

A wheel-like hexadecanuclear cobalt phosphonate [Co(16)(OH)(6)(chp)(22)(O(3)PC(6)H(9))(2)(H(2)O)(4)] has been synthesized by reactions of cobalt perchlorate with cyclohexenephosphonic acid (H(2)O(3)PC(6)H(9)) and 6-chloro-2-hydroxypyridine (Hchp) in the presence of Et(3)N. Magnetic studies on the compound show a general decline of chi(M)T with decreasing T. The appeared maximum of chi(M)T at low temperature suggests the presence of a non-diamagnetic ground state. The alternating current susceptibilities show frequency-dependent signals.

Construction of [Ag2X2]-based complexes from reactions of Ag(I) salts with N-diphenylphosphanylmethyl-4-aminopyridine: isolation, structures, and luminescent properties.

Reactions of N-diphenylphosphanylmethyl-4-aminopyridine (dppmapy) with K[Ag(CN)(2)], Ag(dca) (dca = dicyanamide), AgSCN, AgCl, AgBr or AgI gave rise to six [Ag(2)X(2)]-based (X = CN(-), dca, SCN(-), Cl(-), Br(-) and I(-)) compounds, [{Ag(2)(CN)(2)(dppmapy)}.0.5CHCl(3)](n) (1), [Ag(2)L(2)(dppmapy)(2)](n) (2: L = dca; 3: L = SCN), [{Ag(2)L(2)(dppmapy)(2)}.sol](n) (4: L = Cl, sol = 0.5MeOH.0.5CH(2)Cl(2); 5: L = Br, sol = 2CHCl(3)), and [Ag(2)I(2)(dppmapy)(4)].3MeOH (6). Complexes 1-6 were characterized by elemental analysis, IR, powder X-ray diffraction (PXRD), and single crystal X-ray diffraction. Compound 1 has a one-dimensional (1D) spiral chain constructed by bridging the [(CN)Ag(mu-CN)Ag] fragments via dppmapy ligands. In 2, 3 and 4, each [Ag(2)X(2)] (X = dca, SCN, Cl) fragment is linked by dppmapy bridges to the other two equivalent ones to form a 1D chain containing 16-membered rings (2) or a 1D double chain containing 20-membered rings (3) or a 1D spiral chain containing 20-membered rings (4). Compound 5 possesses a two dimensional (2D) (4,4) network consisting of 36-membered metallomacrocycles in which each [Ag(2)Br(2)] fragment acts as a unique planar four-connecting node to link the other four equivalent ones via dppmapy bridges. Complex 6 has a [Ag(2)I(2)] unit with a pair of monodentate dppmapy ligands coordinated at each Ag center. The photoluminescent properties of 1-6 in the solid state at ambient temperature were also investigated.

Three olefin copper(I) dimeric complexes with 2-, 3-, and 4-pyridylacrylic acid and their electrochemical properties.

UV irradiation of 2-, 3-, or 4-pyridylacrylic acid (2-, 3-, and 4-HPYA) with Cu(I)Cl at 230 nm in 4 N HCl for 1 week and subsequent hydrothermal reactions yielded three novel highly stable 3-D copper(I)-olefin dimers, [(2-H(2)PYA)(2)Cu(+)(2)Cl(4)](n)() (1), [(3-H(2)PYA)(2)Cu(+)(2)Cl(4)](n)() (2), and [(4-H(2)PYA)(2)Cu(+)(2)Cl(4)(I)](n)() (3), respectively, in which H-bonds play a key role in the stabilization of supramolecular Cu(I)-olefin system and thus the formation of the 3-D networks. The electrochemical properties of 1-3 are also reported.