Central-metal exchange, improved catalytic activity, photoluminescence properties of a new family of d(10) coordination polymers based on the 5,5'-(1H-2,3,5-triazole-1,4-diyl)diisophthalic acid ligand.

The rigid and planar tetracarboxylic acid 5,5'-(1H-2,3,5-triazole-1,4-diyl)diisophthalic acid (H4L), incorporating a triazole group, has been used with no or different pyridine-based linkers to construct a family of d(10) coordination polymers, namely, {[H2N(CH3)2]3[Cd3(L)2(HCOO)]}n (), {[Cd2(L)(py)6]·H2O}n (), {[H2N(CH3)2] [Cd2(L)(HCOO)(H2O)4]}n (), {[Zn(H2L)]·H2O}n (), and {[Zn(H2L)(4,4'-bipy)0.5]·C2H5OH·H2O}n () (py = pyridine, 4,4'-bipy = 4,4'-bipyridine). constructs a 3D porous network containing two kinds of channels: one is filled with coordinated HCOO(-) anions, and the other with [H2N(CH3)2](+) cations. The framework of can be described as a rare (5,6,7)-connected net with the Schläfli symbol of (4(12)·5·6(2))(4(5)·5(3)·6(2))2(4(8)·5(3)·6(8)·8(2))2. The Cd(ii) ions in are connected through the carboxylate ligands to form a 2D layer, with aperture dimensions of ∼15.1 Å × 16.2 Å. The network of features a 3D (3,4)-connected (6·8·10)2(6·8(3)·10(2)) topology. A 3D network with the (4(2)·6·8(3)) topology of possesses an open 1D channel with the free volume of 29.2%. is a 2D layer structure with the (4(2)·6(3)·8)(4(2)·6) topology. The fluorescence lifetime τ values of are on the nanosecond timescale at room temperature. In particular, central-metal exchange in leads to a series of isostructural M(ii)-Cd frameworks [M = Cu (), Co (), Ni ()] showing improved catalytic activity for the synthesis of 1,4,5,6-tetrahydropyrimidine derivatives. Based on this, a plausible mechanism for the catalytic reaction has been proposed and the reactivity-structure relationship has been further clarified.

Improved bio-hydrogen production from glucose by adding a specific methane inhibitor to microbial electrolysis cells with a double anode arrangement.

Improved hydrogen production from glucose was achieved by adding a specific methane inhibitor (such as chloroform) to repress the activity of methanogens in a single-chamber microbial electrolysis cells (MECs) with a double anode arrangement. A maximum hydrogen production of 8.4±0.2 mol H2/mol-G (G represents glucose), a hydrogen production rate of 2.39±0.3 m(3) H2/m3/d and a high energy efficiency (relative to the electrical input) of ηE=165±5% had been recorded from 1 g/L glucose at a low dosage of chloroform (5‰, v:v) and an applied voltage of 0.8 V. Almost all of the glucose was removed within 4 h, with 66% of the electrons in intermediates (mainly including acetate and ethanol), and methane gas was not detected in the MECs through 11 batch cycles. The experimental results confirmed that chloroform was an effective methane inhibitor that improved hydrogen production from glucose in the MECs. In addition, the cyclic voltammetry tests demonstrated that the electron transfer in the MECs was mainly due to the biofilm-bound redox compounds rather than soluble electron shuttles.

Surfactant-Assisted Nanocrystalline Zinc Coordination Polymers: Controlled Particle Sizes and Synergistic Effects in Catalysis.

Different morphologies and particle sizes of two crystalline zinc-based coordination polymers (CPs), [Zn(pytz)H2 O]n (1; H2 pytz=2,6-bis(tetrazole)pyridine) and [Zn2 (pytz)2 4 H2 O] (2), from the bulk scale to the nanoscale, could be obtained under solvothermal conditions with different surfactants (polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG) 2000) as templates. PVP and PEG 2000 could act as capping and structure-directing agents, respectively, to influence the growth of crystalline particles and control their sizes. CP 1 exhibits a two-dimensional framework with window-like units and 2 shows a bimetallic structure. Nanocrystalline 1 and 2 were used as heterogeneous catalysts to study how adjacent catalytic active sites synergistically effected their catalytic reactivities in the direct catalytic conversion of aromatic dinitriles into oxazolines. The results showed that 1 produced bis-oxazolines as the sole products, whereas 2 gave the mono-oxazolines as the major products under the same reaction conditions.

A Crystalline Copper(II) Coordination Polymer for the Efficient Visible-Light-Driven Generation of Hydrogen.

A crystalline coordination polymer (CP) photocatalyst (Cu-RSH) which combines redox-active copper centers with photoactive rhodamine-derived ligands remains stable in acid and basic solutions from pH 2 to 14, and efficiently catalyzes dihydrogen evolution at a maximum rate of 7.88 mmol g(-1) h(-1) in the absence of a mediator and a co-catalyst. Cyclic voltammetry, control experiments, and DFT calculations established that copper nodes with open coordination sites and favorable redox potentials, aided by spatially ordered stacking of rhodamine-based linkers, account for the high catalytic performance of Cu-RSH. Emission quenching, time-resolved fluorescence decay, and transient photocurrent experiments disclosed the charge separation and transfer process in the catalytic system. The present study demonstrates the potential of crystalline copper CPs for the practical utilization of light.

Influence of ionic liquids on the syntheses and structures of Mn(II) coordination polymers based on multidentate N-heterocyclic aromatic ligands and bridging carboxylate ligands.

Seven Mn(ii) coordination polymers, namely {[Mn2(ptptp)Cl2(H2O)3]·H2O}n (1), {[Mn(µ-ptptp)3]2[Mn3(µ3-Cl)]2}·2Cl·16H2O (2), {[Mn2(ptptp)(ip)2(H2O)3]·H2O}n (3), {[Mn2(ptptp)(5-CH3-ip)2(H2O)3]·H2O}n (4), {[Mn4(ptptp)(5-Br-ip)3(H2O)3]·4H2O}n (5), {[Mn2(ptptp)(Hbtc)(H2O)2]·2H2O}n (6) and {[Mn2(ptptp)(tdc)(H2O)2]·1.5H2O}n (7), have been prepared based on multidentate N-heterocyclic aromatic ligands and bridging carboxylate ligands (H2ptptp = 2-(5-{6-[5-(pyrazin-2-yl)-1H-1,2,4-triazol-3-yl]pyridin-2-yl}-1H-1,2,4-triazol-3-yl)pyrazine; R-isophthalic acids, H2ip-R: R = -H (3), -CH3 (4), -Br (5); H3btc = trimesic acid (6); H2tdc = thiophene-2,5-dicarboxylic acid (7)), in order to further probe the multiple roles of [RMI]Br ionic liquids in the hydro/solvothermal synthesis (RMI = 1-alkyl-3-methylimidazolium, R = ethyl, or propyl, or butyl). The successful syntheses of complexes 2-6 suggest that in hydro/solvothermal synthesis the addition of a small amount of [RMI]Br plays a crucial role. Complex 1 exhibits single right-handed helices constructed by ptptp ligands and Mn(ii) ions. Complex 2 possesses octanuclear helicate structures in which two propeller-shaped [Mn(µ-ptptp)3](4-) units embrace two [Mn3(µ3-Cl)](5+) cluster cores inside. Complexes 3 and 4 are isostructural and display a 1D double chain formed by two kinds of pseudo meso-helices: (Mn-ptptp)n and (Mn-5-R-ip)n. Complex 5 has a 2D structure containing 1D Mn(ii) ion chains formed through carboxylates and [ptptp](2-)-N,N bridges. Complex 6 shows a 2D structure formed by a meso-helix (Mn-ptptp)n and the partly deprotonated Hbtc ligands. Complex 7 features a heterochiral [2 + 2] coaxially nested double-helical column formed by using the outer double-helices (Mn-ptptp)n as a template to encapsulate the inner double-helices (Mn-tdc)n with opposite orientation. All complexes were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, single-crystal X-ray crystallography and powder X-ray diffraction. The magnetic properties of 1-7 were also investigated.

Effective conversion of maize straw wastes into bio-hydrogen by two-stage process integrating H2 fermentation and MECs.

The enhanced H2 production from maize straw had been achieved through the two-stage process of integrating H2 fermentation and microbial electrolysis cells (MECs) in the present work. Several key parameters affecting hydrolysis of maize straw through subcritical H2O were optimized by orthogonal design for saccharification of maize straw followed by H2 production through H2 fermentation. The maximum reducing sugar (RS) content of maize straw reached 469.7 mg/g-TS under the optimal hydrolysis condition with subcritical H2O combining with dilute HCl of 0.3% at 230 °C. The maximum H2 yield, H2 production rate, and H2 content was 115.1 mL/g-TVS, 2.6 mL/g-TVS/h, and 48.9% by H2 fermentation, respectively. In addition, the effluent from H2 fermentation was used as feedstock of MECs for additional H2 production. The maximum H2 yield of 1060 mL/g-COD appeared at an applied voltage of 0.8 V, and total COD removal reached about 35%. The overall H2 yield from maize straw reached 318.5 mL/g-TVS through two-stage processes. The structural characterization of maize straw was also carefully investigated by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) spectra.

The effect of metal ions on photocatalytic performance based on an isostructural framework.

A series of 2D layered isostructural coordination complexes {[M3(L)2(H2O)6]·H2O}n (M = Mn (1), Mn0.7Co0.3 (2), Mn0.5Co0.5 (3), Mn0.3Co0.7 (4), and Co (5), respectively, H3L = 1-aminobenzene-3,4,5-tricarboxylic acid) have been synthesized under hydrothermal conditions, and applied to catalyze the reaction of degenerating organic dyes under visible light irradiation. The photocatalytic results indicate that complex 5 exhibits good photocatalytic properties in the presence of H2O2, while 1 can restrain the photodegradation of organic dyes. Remarkably, when Mn ions are gradually replaced by Co ions in the complexes, the photocatalytic activities of 1­5 turn from inhibition to promotion, which is a controllable regulation of photocatalytic properties via changing metal ions. Moreover, by using novel magnetic analysis methods and diffuse-reflectance UV/Vis spectra analysis methods, we explain the influence of central metal ions on the photocatalytic performance.

Direct degradation of cellulosic biomass to bio-hydrogen from a newly isolated strain Clostridium sartagoforme FZ11.

A mesophilic hydrogen-producing strain, Clostridium sartagoforme FZ11, had been newly isolated from cow dung compost acclimated using microcrystalline cellulose (MCC) for at least 30 rounds in an anaerobic bioreactor, and identified by the 16S rDNA gene sequencing, which could directly utilized various carbon sources, especially cellulosic biomass, to produce hydrogen. The maximum hydrogen yields from MCC (10 g/l) and carboxymethyl cellulose (CMC, 10 g/l) were 77.2 and 64.6 ml/g, separately. Furthermore, some key parameters of affecting hydrogen production from raw corn stalk were also optimized. The maximal hydrogen yield and substrate degradation rate from raw corn stalk were 87.2 ml/g and 41.2% under the optimized conditions with substrate concentration of 15 g/l, phosphate buffer of 0.15 M, urea of 6 g/l and initial pH of 6.47 at 35 °C. The result showed that the strain FZ11 would be an ideal candidate to directly convert cellulosic biomass into bio-hydrogen without substrate pretreatment.

Reversible conversion of valence-tautomeric copper metal-organic frameworks dependent single-crystal-to-single-crystal oxidation/reduction: a redox-switchable catalyst for C-H bonds activation reaction.

Upon single-crystal-to-single-crystal (SCSC) oxidation/reduction, reversible structural transformations take place between the anionic porous zeolite-like Cu(I) framework and a topologically equivalent neutral Cu(I)Cu(II) mixed-valent framework. The unique conversion behavior of the Cu(I) framework endowed it as a redox-switchable catalyst for the direct arylation of heterocycle C-H bonds.

Spectroscopic and crystallographic investigations of novel BODIPY-derived metal-organic frameworks.

To explore new 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-derived metal-organic frameworks (MOFs), we employed 2,6-dicarboxyl-1,3,5,7-tetramethyl-8-phenyl-4,4-difluoroboradiazaindacene (H2L) as a ligand to successfully synthesize five coordination polymers, namely, {[Zn2(L)2(bpp)]·2H2O·2EtOH}n (1), {[Cd2(L)2(bpp)]·2H2O·EtOH}n (2), {[Cd2(L)(bpe)3(NO3)2]·2H2O·DMF·EtOH}n (3), {[Cd(L)(bpe)0.5(DMF)(H2O)]}n (4), and {[Cd(L)(bpe)0.5]·1.5H2O·DMF}n (5) (bpp = 1,3-bi(4-pyridyl)propane, bpe = 1,2-bi(4-pyridyl)ethane). Except for two 2D-layer coordination polymers 3 and 4, the rest samples exhibit 3D metal-organic frameworks with certain pore sizes, especially MOFs 1 and 5. Spectroscopic and crystallographic investigations demonstrate that the absorption and emission energies of the BODIPY chromophores are sensitive to the coordination modes. Moreover, in case 2, the transition metal centers coordinated with the dicarboxylate ligands L(2-) are capable of forming the two BODIPY units in coplanar arrangements (θ = 37.9°), simultaneously suppressing the uncommon J-dimer absorption band centered at 705 nm with a long tail into the near-infrared region at room temperature. On the other hand, in comparison with the ligand H2L, the emission of monomer-like BODIPY in case 3 is enhanced in the solid state by a considerably long distance between the parallel BODIPY planes (about 14.0 Å).

Solvent templates induced porous metal-organic materials: conformational isomerism and catalytic activity.

Solvent templates induced Co-based metal-organic materials; conformational isomers {[Co2(pdpa)(CH3CN)(H2O)3]·CH3OH·H2O}n (1) and {[Co2(pdpa)(CH3CN)(H2O)3]}n (2) and {[Co5(pdpa)2(µ3-OH)2(H2O)6]·2H2O}n (3) [H4pdpa = 5,5'-(pentane-1,2-diyl)-bis(oxy)diisophthalic acid] were synthesized under the same solvothermal conditions except with different concentrations of cyclic ethers (1,4-dioxane or tetrahydrofuran) as structure-directing agents. Structural transformations from a three-dimensional (3D) framework of 1 containing channels with dimensions of ∼6 Å × 6 Å to a two-dimensional layer structure of 2 consisting of large open channels with a size of ∼15 Å × 8 Å and then to a 3D nonporous framework of 3, resulting from the different concentrations of cyclic ethers, were observed. The anion-π interactions between electron-efficient oxygen atoms of cyclic ethers and electron-deficient dicarboxylic acid aromatic cores in H4pdpa imported into the synthetic process accounted for the conformational change of the ligand H4pdpa and the following structural variations. A systematic investigation was conducted to explore how different concentrations of structure-directing agents affected the frameworks of resultant metal-organic frameworks. Furthermore, 1-3 were shown to be available heterogeneous catalysts for the synthesis of 2-imidazoline and 1,4,5,6-tetrahydropyrimidine derivatives by the cascade cycloaddition reactions of aromatic nitriles with diamines. The results showed that the catalytic activity of 2 was much higher than that of 1 and 3, because of its unique structural features, including accessible catalytic sites and suitable channel size and shape. In addition, a plausible mechanism for these catalytic reactions was proposed, and the reactivity-structure relationship was further clarified.

Copper(II) coordination polymers: tunable structures and a different activation effect of hydrogen peroxide for the degradation of methyl orange under visible light irradiation.

By tuning the synthesis conditions, based on a conformation-sensitive ligand, 1,4-bis(1,2,4-triazole-1-methylene)-2,3,5,6-tetramethyl benzene (btmx) and Cu(NO3)2·3H2O/CuCl2·2H2O, we have obtained three Cu(ii) coordination polymers with diverse structures, namely, {[Cu(btmx)2(H2O)]·2NO3}n (), {[Cu(btmx)2(Cl)2]·5H2O}n () and [Cu(btmx)(Cl)2]n (). Complex exhibits a novel 2D → 3D interpenetrating structure with a point symbol of 6(3). Complex features an irregular 2D grid with (4(4)·6(2)) topology. The structure of complex is a 1D double chain structure. The ultraviolet-visible absorption spectra and TG curves of these complexes are also presented and discussed. Moreover, under visible light, the coordination polymers , , and display a different activation effect of hydrogen peroxide (H2O2) for the photocatalytic decomposition of methyl orange (MO), which indicates that the coordination polymers may have bright prospects in the field of photocatalytic degradation of dyes.

Template-induced diverse metal-organic materials as catalysts for the tandem acylation-Nazarov cyclization.

In our continuing quest to develop a metal-organic framework (MOF)-catalyzed tandem pyrrole acylation-Nazarov cyclization reaction with α,ß-unsaturated carboxylic acids for the synthesis of cyclopentenone[b]pyrroles, which are key intermediates in the synthesis of natural product (±)-roseophilin, a series of template-induced Zn-based (1-3) metal-organic frameworks (MOFs) have been solvothermally synthesized and characterized. Structural conversions from non-porous MOF 1 to porous MOF 2, and back to non-porous MOF 3 arising from the different concentrations of template guest have been observed. The anion-π interactions between the template guests and ligands could affect the configuration of ligands and further tailor the frameworks of 1-3. Futhermore, MOFs 1-3 have shown to be effective heterogeneous catalysts for the tandem acylation-Nazarov cyclization reaction. In particular, the unique structural features of 2, including accessible catalytic sites and suitable channel size and shape, endow 2 with all of the desired features for the MOF-catalyzed tandem acylation-Nazarov cyclization reaction, including heterogeneous catalyst, high catalytic activity, robustness, and excellent selectivity. A plausible mechanism for the catalytic reaction has been proposed and the structure-reactivity relationship has been further clarified. Making use of 2 as a heterogeneous catalyst for the reaction could greatly increase the yield of total synthesis of (±)-roseophilin.

Metal-organic frameworks based on the [1,1':3',1''-terphenyl]-3,3'',5,5''-tetracarboxylic acid ligand: syntheses, structures and magnetic properties.

The solvothermal reactions of [1,1':3',1''-terphenyl]-3,3'',5,5''-tetracarboxylic acid (H4TPTA) with transition metal cations afforded five novel coordination polymers in the presence of three pyridine ligands (4,4'-bipy = 4,4'-bipyridine, 2,2'-bipy = 2,2'-bipyridine and phen = 1,10-phenanthroline), namely [M(TPTA)0.5(4,4'-bpy)0.5(H2O)2]n (M = Co for (1), Ni for (2)), {[Mn2(TPTA)(2,2'-bpy)H2O]·1.5H2O}n (3), and [M(H2TPTA)(phen)]n (M = Mn for (4), Co for (5)). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Polymers 1 and 2 are isomorphous and exhibit 3D 4-fold interpenetrated networks with the point Schläfli symbol of (4(2)·10(4)) (4·10(2)). Polymer 3 shows a 2D layer framework. Polymers 4 and 5 are also isomorphous and each displays a one-dimensional (1D) chain, which further forms a 2D supramolecular architecture via inter-chain π···π interactions. Moreover, variable-temperature magnetic susceptibilities of polymers 3-5 exhibit overall weak antiferromagnetic coupling between the adjacent M(II) ions.

Structural variability, topological analysis and photocatalytic properties of neoteric Cd(II) coordination polymers based on semirigid bis(thiazolylbenzimidazole) and different types of carboxylic acid linkers.

A series of novel Cd(II) coordination complexes, formulated as {[Cd(btbb)0.5(p-phda)]·H2O}n (), [Cd(btbb)0.5(oba)]n (), {[Cd2(btbb)(m-bdc)2(H2O)]·2H2O}n (), {[Cd(btbb)0.5(btec)0.5(H2O)]·2H2O}n (), [Cd(btbb)0.5(o-bdc)]n () and {[Cd2(btbb)(bptc)(H2O)]·4H2O}n () (btbb = 1,4-bis(2-(4-thiazolyl)benzimidazol-1-ylmethyl)benzene, H2phda = phenylenediacetic acid, H2oba = 4,4'-oxybis(benzoic acid), m-H2bdc = 1,3-benzenedicarboxylic acid, H4btec = 1,2,4,5-benzenetetracarboxylate, o-H2bdc = 1,2-benzenedicarboxylic acid, H4bptc = 3,3',4,4'-benzophenone tetracarboxylic acid), have been obtained by solvothermal/hydrothermal reactions for the exploration of efficient photocatalytic degradation of organic dye pollutants. Complex features a 6-connected 3D pcu α-Po primitive cubic topology net with the point symbol 4(12)·6(3). Interestingly, complexes , and contain left- and right-handed helical chains (: a 2-fold interpenetrating 3D architecture with {4(12)·6(3)}-pcu topology network; : a (3,6)-connected net with a vertex symbol (4(2)·5(4)·6(6)·7·8(2))(4·6(2)); : a (3,4)-connected 3,4L83 topology net with point symbol (4(2)·6)(4(2)·6(3)·8)). Complex exhibits a (3,4)-connected 3,4T48 topology net with point symbol (8(4)·10(2))(8·10(2)), while complex possesses a (3,5)-connected 3,5L2 topology with the point symbol (4(2)·6)(4(2)·6(7)·8). Furthermore, the photophysical studies indicate that the relatively narrow optical energy gaps of complexes (<2.30 eV) calculated from the diffuse reflectivity spectra reflect their outstanding semiconductive nature. The photocatalytic properties of complexes were studied in detail, and the results demonstrate their good photocatalytic activities in methylene blue (MB) degradation reactions, especially for complexes , and (: 91.4%, : 92.7%, : 86.7%).

Guest molecule release triggers changes in the catalytic and magnetic properties of a Fe(II)-based 3D metal-organic framework.

A Fe(II)-based metal-organic framework (MOF), {[Fe2(pbt)2(H2O)2]·2H2O}n, undergoes an irreversible dehydration, which triggers changes in the catalytic and magnetic properties of the MOF. These property changes are attributed to the high-spin to low-spin transition of 7.1% center Fe(II), which is demonstrated by (57)Fe Mössbauer, X-ray photoelectron spectroscopy, and UV/vis absorption spectra.

New mechanistic insight into stepwise metal-center exchange in a metal-organic framework based on asymmetric Zn(4) clusters.

Herein, a mechanism of stepwise metal-center exchange for a specific metal-organic framework, namely, [Zn4 (dcpp)2 (DMF)3 (H2 O)2 ]n (H4 dcpp=4,5-bis(4'-carboxylphenyl)phthalic acid), is disclosed for the first time. The coordination stabilities between the central metal atoms and the ligands as well as the coordination geometry are considered to be dominant factors in this stepwise exchange mechanism. A new magnetic analytical method and a theoretical model confirmed that the exchange mechanism is reasonable. When the metathesis reaction occurs between Cu(II) ions and framework Zn(II) ions, the magnetic exchange interaction of each pair of Cu(II) centers gradually strengthens with increasing amount of framework Cu(II) ions. By analyzing the changes of coupling constants in the Cu-exchanged products, it was deduced that Zn4 and Zn3 are initially replaced, and then Zn1 and Zn2 are replaced later. The theoretical calculation further verified that Zn4 is replaced first, Zn3 next, then Zn1 and Zn2 last, and the coordination stability dominates the Cu/Zn exchange process. For the Ni/Zn and Co/Zn exchange processes, besides the coordination stability, the preferred coordination geometry was also considered in the stepwise-exchange behavior. As Ni(II) and Co(II) ions especially favor octahedral coordination geometry in oxygen-ligand fields, Ni(II) ions and Co(II) ions could only selectively exchange with the octahedral Zn(II) ions, as was also confirmed by the experimental results. The stepwise metal-exchange process occurs in a single crystal-to-single crystal fashion.

Direct bioconversion of raw corn stalk to hydrogen by a new strain Clostridium sp. FS3.

A new strain FS3 which could achieve an efficient bioconversion of raw corn stalk to hydrogen had been isolated from anaerobic acclimated sludge, and identified as Clostridium butyricum on the basis of a series of physiological and biochemical experiments and 16S rDNA gene sequence. The strain could utilize various carbon sources to produce hydrogen. On the basis of single-factor experiments, the response surface methodology (RSM) was performed to optimize the media for hydrogen production. The maximum hydrogen yield of 92.9ml/g was observed under the optimal conditions: 20g/l raw corn stalk, 1.76g/l NH4HCO3, 0.91g/l KH2PO4 and 10.4ml/l nutrient solution. This finding opens a new avenue for direct conversion of raw cellulosic biomass to bio-hydrogen.

Conversion from a heterochiral [2 + 2] coaxially nested double-helical column to a cationic spiral staircase stimulated by an ionic liquid anion.

The conversion from a [2 + 2] nested double-helical column, {[Mn2(ptptp)(suc)(H2O)2]·1.5H2O}n (1), to a cationic spiral staircase, {[Mn2(ptptp)(suc)0.5(H2O)3]·Br·0.5H2O}n (2), has been achieved through ionic liquid anion stimulations under solvothermal conditions. The conversion does not change the antiferromagnetic interactions.

Photocatalytic H2 generation based on noble-metal-free binuclear cobalt complexes using visible-light.

Two new binuclear cobalt complexes, namely {[Co(dmgH)(dmgH2)]2L1} (I) and {[Co(dmgH)(dmgH2)]2L2} (II) (dmgH = dimethylglyoximate monoanion; dmgH2 = dimethylglyoxime, L1 = 1,3-bis(4-pyridyl)propane), L2 = 1,3-bis(imidazol-1-ylmethyl)benzene), have been synthesized by the self-assembly of [Co(dmgH)(dmgH2)] and L1 or L2, respectively. An efficient photocatalytic system was constructed by combining a noble-metal-free cobalt complex as the catalyst with Eosin Y dye (EY(2-)) as the photosensitizer to give an efficient H2 generating system under visible-light irradiation (λ > 420 nm) using triethanolamine (TEOA) as a sacrificial electron donor. The maximum amount of H2 generated was 1013 TON for I and 1134 TON for II over a 2 h irradiation period (λ > 420 nm) under the conditions of pH 8.0, 5% TEOA (v/v), an EY(2-) concentration of 4.0 × 10(-4) M and a catalyst concentration of 4.0 × 10(-4) M in the mixed solvent system of CH3CN-H2O (3 : 1, v/v). In addition, the mechanism of H2 generation in the photolysis system was briefly discussed.