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C30H36F2N6O9S, orthorhombic, P212121 (no. 19), a = 5.2364(8) Å, b = 10.0250(14) Å, c = 59.689(9) Å, V = 3133.4(8) Å3, Z = 4, Rgt (F) = 0.0384, wRref (F 2) = 0.0969, T = 170 K.

The synthesis, structures and properties of three new Zn2+-trimesate (BTC3−) coordination polymers (CPs), {[Zn(BTC) (NH3)2]·2H2O}n (1), {[Zn3(BTC)2(NH3)2(H2O)6]·2H2O}n (2) and {[Zn3(BTC)2(NH3)6]·5H2O}n (3), have been reported. They were isolated under the ammoniacal circumstance by dissolving 1,3,5-benzenetricarboxylic acid (H3BTC) and zinc acetate in different mixed-solvents. The three CPs were comprehensively characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, elemental analysis and Fourier Transform Infrared analysis. Their photoluminescence properties were also studied. The results reveal that solvents play important roles on the structures and topologies of the obtained CPs. The crystallographic studies manifest that the CPs 1–3 are 1D chain, 1D ladder and 2D layer structures, respectively.

Three series of copper hydride clusters [Cu8H6L6]2+ (1), [Cu4HX2L4]+ where X− = Cl− (2a), Br− (2b), I− (2c), N3− (2d) and SCN− (2e), and [Cu4HX3L3] where X− = Br− (3b) and I− (3c) (L = 2-(diphenylphosphino)pyridine, dppy) were synthesized and characterized by single-crystal X-Ray crystallography and standard spectroscopic techniques. The metal core of 1, Cu8, can be described as a bicapped octahedron, while those of 2 and 3 series adopt tetrahedral structures. The hydride positions were deduced from difference electron density maps and corroborated by NMR and DFT calculations. For 1, there are two μ4-H−, one each in the two tetrahedral cavities of the two capping atoms and four μ3-H− on the six triangular faces around the waist of the octahedron. For [Cu4HX2L4]+ and [Cu4HX3L3] series, the single μ4-H− resides in the center of the Cu4 tetrahedron. It was found that these three series of copper clusters are intimately connected and can convert from one to another under specific reaction conditions. Their transformation pathways were investigated in detail. Spontaneous resolution to form optically pure enantiomeric single crystals was observed for [Cu4H(SCN)2L4]+ (2e) and [Cu4HBr3L3] (3b). Photoluminescence was observed for [Cu4HX2L4]+, as well as [Cu4HX3L3] with strong emissions from green to yellow regions.

Four silver(I) coordination polymers (CPs), namely {Ag3(cpyz)(btc)}n (1), {Ag2(cpyz)(pta)}n (2), {Ag3(mpyz)2(btc)·2(H2O)}n (3), {Ag2(mpyz)(pta)·2(H2O)}n (4), [cpyz = 2-chloropyrazine, H3btc = 1,3,5-benzene tricarboxylic, mpyz = 2,6-dimethylpyrazine, H2pta = phthalic acid] have been synthesized and characterized. X-ray diffraction indicates that, 1 shows a 3D supramolecular structure with a 1D silver chain containing an infinite Ag3 units; 2 features a 3D supramolecular framework with Ag-O and Ag-Ag interaction and cpyz ligand adopts monodentate mode making no contribution to the dimensionality; in 3, the silver atom links mpyz ligand and btc anion into a 2D layer connected by Ag-Ag interaction between neighboring layers into the 3D network, with Zigzag Ag4 units; in 4, Ag(I) coordinates pta benzene dicarboxylates to generate a one-dimensional infinite chain, connecting by nitrogen ligand to exhibit a 2D 44-sql network. The results suggest that benzene dicarboxylates and the kinds of pyrazine derivatives play significant roles in the formation of such coordination architectures. The photoluminescence and thermogravimetric analysis (TGA) of the complexes were measured.

Four silver(I) coordination polymers based on 2,6-dimethylpyrazine(dmpz), {Ag2(dmpz)(L1)}n (1), {Ag2(dmpz)(L2)}n (2), {Ag2(dmpz)(L3)0.5·H2O}n (3) and {Ag6(dmpz)6(L4)2·2H2O}n (4) (H2L1 = 5-Nitroisophthalic acid, H2L2 = 3-Nitrophthalic acid, H4L3 = Pyromellitic acid, H2L4 = 5-Sulfoisophthalic acid), were synthesized under the ammoniacal condition in mixed solvents and characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. 1 contains rhombic Ag4 unit, but 4 exhibits Zigzag Ag4 unit, both with 2D double layer architecture. In 2, L2 anions link Ag pairs into 1D corrugated chains, which are further connected by dmpz ligand into 2D 44-sql network. 3 possess 3D supramolecular framework resulting from Ag O and Ag N interaction and Zigzag Ag4 units. Ag Ag interactions exist in four coordination polymers. Benzene dicarboxylates and pyrazine ligands play vital roles in formation of the multiple architectures. Photoluminescence and thermogravimetry of the complexes were also measured.

Two fullerene C 60 derivatives, 2-(3-ethoxycarbonylpropyloxy)-(5,8)-dihydronaphthyl-(6,7)-[6,6]-C 60 (EDNC) and 2-benzyloxy-(5,8)-dihydronaphthyl-(6,7)-[6,6]-C 60 (BDNC), are introduced into p-i-n type planar heterojunction perovskite solar cells as electron transport materials (ETMs) to investigate electrochemical, charge-transporting, and film-forming properties of fullerene ETMs and the resulting photovoltaic performance in comparison with [6,6]-phenyl-C 61 -butyric acid methyl ester (PC 61 BM). Due to better surface morphology, the EDNC-involving device shows better performance (12.64%) than that of BDNC-based device (7.36%) despite of their similar LUMO energy level, electron mobility, optical properties, and electrochemical properties. Higher power conversion efficiency (PCE) of 15.04% is achieved using PC 61 BM as the ETM, the electronic mobility of PC 61 BM is approximately one order of magnitude higher than that of EDNC, which leads to slightly higher short-circuit current density and fill factor for PC 61 BM-based device. This work demonstrates that factors such as electron mobility and surface morphology should be envisaged in searching for fullerene derivatives as efficient ETM in perovskite solar cells.

The demand on the highly efficient and low-cost cathodic electrocatalysts for commercialization of fuel cells is rapidly increasing. One smart route for obtaining these ideal electrocatalysts is extracting active carbon materials from natural and cheap biomass waste. Here, we prepared a novel nitrogen self-doped porous graphitic carbon nanosheets (NPGCNs-NaCl) derived from a nitrogen-rich pruning of Lycium barbarum L. using NaCl crystal as intercalation agent. The as-obtained NPGCNs-NaCl possessed porous structure, large surface area, increased content of nitrogen and high graphitic carbon, and thus making it with high electrocatalytic activity for oxygen reduction reaction (ORR). Most importantly, significantly enhanced stability and tolerance against methanol were observed compared with commercial Pt/C catalyst in alkaline solution. This work is believed to open a new avenue for manufacturing advanced and low-cost ORR electrocatalysts in fuel cells from biomass waste.

Organic–inorganic perovskite solar cells have emerged as a promising photovoltaic technology because of their advantages such as low cost, high efficiency, and solution processability. The performance of perovskite solar cells is highly dependent on the crystallinity and morphology of the perovskite films. Herein, we report a simple, one-step anti-solvent deposition process using di-isopropyl ether as a dripping solvent to obtain extremely uniform and highly crystalline CH3NH3PbI3 perovskite films. Compared to toluene, chlorobenzene, chloroform, or diethyl ether, di-isopropyl ether has proven to be a more suitable solvent for an anti-solvent deposition process. The perovskite solar cells fabricated by the anti-solvent deposition process using di-isopropyl ether treatment exhibit an average power conversion efficiency (PCE) of 17.67 ± 0.54% and the highest PCE of 19.07%. Moreover, the higher boiling point of di-isopropyl ether makes the anti-solvent deposition process more tolerant to elevated ambient temperature, which can be carried out at ambient temperatures up to 40 °C. Our results demonstrate that di-isopropyl ether is an excellent dripping solvent in the anti-solvent deposition process for efficient and reproducible perovskite solar cells.

In high performance perovskite solar cells (PSCs), the electron transport layer (ETL) has overwhelmingly been dominated by compact titanium oxide (TiO2), which typically requires sintering at around 500 °C. Such a high-temperature sintering procedure prevents TiO2-based PSCs from matching well with plastic substrates and low-cost manufacturing. Here we report cerium oxide (CeOx, x = 1.87), that was prepared facilely through a simple sol–gel method at low temperature (∼150 °C), as an alternative to high-temperature sintering processed TiO2 in the regular architecture of PSCs. With a PCE of 14.32% from the involvement of an optimized CeOx ETL through adjusting the precursor solution, and a higher PCE of 17.04% through introducing a [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) interfacial layer between the CeOx ETL and the perovskite layer, the present work about CeOx-based PSCs renders low-temperature solution-processed CeOx an excellent ETL for high performance perovskite solar cells with improved stability.

Filiació URV: SI As a bridge to connect medium-sized fullerenes, fused-pentagon C74 is still missing heretofore. Of 14-246 possible isomers, the first fused-pentagon C74 with the Fowler-Manolopoulos code of 14-049 was stabilized as C74Cl10 in the chlorine-involving carbon arc. The structure of C74Cl10 was identified by X-ray crystallography. The stabilization of pristine fused-pentagon C74 by stepwise chlorination was clarified in both theoretical simulation with density functional theory calculations and experimental fragmentation with multistage mass spectrometry.

Four mixed-ligand silver(I) coordination polymers (CPs) {Ag2(tpyz)(L)}_n (1), {Ag4(tpyz)2(L)2}_n (2), {Ag2(mpyz)(L)}_n (3) as well as its isomer (4), (tpyz-2,3,5-trimethylpyrazine, mpyz = 2,3,5,6-tetramethylpyrazine, H2L = (+)-camphoric acid), were synthesized with reactions of L and pyrazine derivatives with silver nitrate in different solvent systems. Systematic characterizations with single-crystal X-ray diffraction indicate that, 1 and 3 show a 3D framework which constructed by silver(I) and L anion, the pyrazine derivatives only give one N to connect to metal, which may be due to the disorder of the methyl which shares the same carbon with carboxylate; 2 and 4 demonstrate a 2D 4 4–sql network. The difference between two: one structure is single layer and the other is double layer. Furthermore, 4 contains a 1D helical chains which connected by Ag(I) and mpyz ligand. Meanwhile, the L anion exhibits different coordination modes in 1–4. 1–4 spanning from two-dimensional network to three-dimensional framework suggest that the kinds of pyrazine derivatives and solvents play significant roles in the formation of such coordination architectures. The thermogravimetric analyses (TGA), IR, and photoluminescence were also measured.

Three mix-ligand Ag(I) coordination compounds, namely, {[Ag10(tpyz) 5(L1) 5(H2 O)2].(H2 O)4}n (1, tpyz = 2,3,4,5-tetramethylpyrazine, H2 L1 = phthalic acid), [Ag4(tpyz) 2(L2) 2(H2 O)].(H2 O)5}n (2, H2 L2 = isophthalic acid) {[Ag2(tpyz) 2(L3) (H2 O)4].(H2 O)8}n (3, H2 L3 = terephthalic acid), have been synthesized and characterized by elemental analysis, IR, PXRD and X-ray single-crystal diffraction. 1 exhibits a 2D layer which can be simplified as a (4,4) net. 2 is a 3D network which can be simplified as a (3,3)-connected 2-nodal net with a point symbol of {102.12}{102}. 3 consists of linear [Ag(tpyz) (H2 O)2]n chain. Of particular interest, discrete hexamer water clusters were observed in 1 and 2, while a 2D L10(6) water layer exists in 3. The results suggest that the benzene dicarboxylates play pivotal roles in the formation of the different host architectures as well as different water aggregations. Moreover, thermogravimetric analysis (TGA) and emissive behaviors of these compounds were investigated.

Six coordination compounds of Ag(I) and 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine (L, Ag:L = 1:2) with different anions and solvents, namely, [Ag(L)2]∙(NO3)∙4(H2O) (1), [ Ag ( L ) 2 ] · 1 / 2 ( nds ) · ( MeOH ) · ( H 2 O ) (2, H2nds = 1,5-naphthalenedisulfonic acid), [ Ag ( L ) 2 ] · 1 / 2 ( nds ) · ( MeOH ) · 5 / 2 ( H 2 O ) (3), [ Ag ( L ) 2 ] · 1 / 2 ( nds ) · ( CH 3 CN ) (4), [Ag(L)2]∙(ClO4)∙(MeOH)∙(H2O) (5), and [Ag(L)2]∙(ClO4)∙2(H2O) (6), have been synthesized and characterized by elemental analysis, IR, PXRD and X-ray single-crystal diffraction. In these compounds, each Ag(I) ion is ligated by two imidazole nitrogens to form a Ag(L)2 unit. The anions and solvents determine hydrogen-bonding between the DAT groups links the Ag(L)2 units whether to form chains in 1 and 2 or layers in 3–6. In addition, thermogravimetric analysis (TGA) and luminescent properties of these compounds were also investigated.

Three Cu(Ⅱ) coordination compounds (CCs) with 4,4′-oxybisbenzoic acid (H2OBBA), {Cu3(OBBA)2(NH3)4}n (1), {Cu(OBBA)0.5(NH3)}n (2), {Cu2(OBBA) (NH3) (OH)}n (3) were synthesized under the ammoniacal condition in mixed solvents and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis and Fourier transform infrared spectra. Crystallographic studies have shown that, CC 1 is a 1D wavy chain structure, while the intermolecular connection of hydrogen bonds made it a 2D layered structure; CC 2 is a 2D layered structure composed of a 1D wavy chain structure and the O–H⋯N hydrogen bonds of R (2)2 (12) hydrogen bond motifs; CC 3 forms a 3D supramolecular framework through OH−, OBBA ligand and hydrogen bonds, in which, OBBA ligand has two cyclic patterns: C–OM―O and C–O―M, O⋯H–N. It may be concluded that OBBA ligands and hydrogen bonds play important role in the formation of multiple architectures. The photoluminescence and thermal behavior were also studied.

Five one-dimensional to three-dimensional coordination polymers have been synthesized by 2-chlorobenzoic acid (HL1), 2-nitrobenzoic acid (HL2), o-toluic acid (HL3), 2,3,5-trimethylpyrazine (tpyz) and 2,3,5,6-tetramethylpyrazine (mpyz) in the presence of NH3·H2O in mixed solvents systems, namely, {Ag4(tpyz)2(L1)4}n (1), {Ag2(tpyz) (L2)2}n (2), {Ag2(tpyz) (L3)2}n (3), {Ag2(mpyz) (L1)2}n (4), {Ag(mpyz) (L2) (H2O)}n (5). All the complexes have been characterized by elemental analyses, IR spectra and X-ray diffraction. Compound 1 shows a 3D framework. The tpyz ligand links 1D chain which was connected by silver atom and L1 anion into 3D framework. Compounds 2 and 4 possess a similar 2D network with (4, 4) topology. Complex 3 also exhibits a two-dimensional structure. There is a 1D silver chain in 3, which is the main difference from 2 and 4. So, 3 shows three-connected (4 8, 3) topology. For 5, only one oxygen of L2 coordinated to Ag(I) ions. The L2 anions were arranged in both sides of the chain, which was connected by silver atoms and mpyz ligands. Then, the uncoordinated carboxylate oxygen with coordinated water 1molecule oxygen through the hydrogen bond made the resultant structure to a 3D framework. Complexes 1–5 spanning from one-dimensional chains to three-dimensional framework suggest that carboxylates and the kinds of pyrazine derivatives play significant roles in the formation of such coordination architectures. The photoluminescence and thermogravimetric analysis (TGA) of the complexes were also investigated.

Three new silver(I) coordination compounds based on 2-ethyl-3-methylpyrazine (epyz), [Ag2(epyz)(pta] (1), [Ag4(epyz)2(ipa)2] (2) and [Ag8(epyz)4(npa)4] (3, H2pta = o-phthalic acid, H2ipa = m-phthalic acid, H2npa = 1,4-napthalenedicarboxylic acid), have been synthesized and have been characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. Complex 1 shows a two-dimensional network comprising Ag2 units linked by the organic ligands. In complex 2, tetrahedral Ag4 units are bridged by the organic linkers into a double-layer structure. In complex 3, the chains with alternating Ag3 and Ag5 units are connected by the organic ligands into a three-dimensional framework. The structural diversity of these compounds and the Ag units is highly dependent on different carboxylates and the coordination modes of the epyz ligand. The thermal stabilities and photoluminescence behaviors of these complexes were also discussed.

Reaction of a flexible ligand 2,4-diamino-6-[2-(2-methyl-1-imidazolyl) ethyl]-1,3,5-triazine (L) with Ag(I) in the presence of different counteranions afforded five complexes, namely, 2[Agn(L)n(NH3)n] · n[Ag2(L)2(NH3)2] · 2n(nds) (1, H2nds = 1,5-naphthalenedisulfonic acid), 2[Agn(L)n] · n[Ag2(L)2(CF3CO2)2] · nCF3CO2 (2), [Ag2(L)2(NH3)2] · 2(ClO4) (3), [Ag2(L)2] · 2(NO3) (4), [Ag2(L)2] · 2(ClO3) (5), which were characterized by element analysis, IR, PXRD and X-ray single-crystal diffraction. Structural analysis reveals that the L ligand take the same bidentate coordination mode in these complexes. The nds anion and the CF3 CO 2 - anion lead to the coexistence of isomeric metallacycle and helical chain (ring-opening isomers) in the crystals of 1 and 2, while ClO 4 - , NO 3 - and ClO 3 - anions afford dimeric metallacycles in complexes 3–5. Moreover, thermal gravity analysis (TGA) and emissive behaviors of these complexes were investigated.

Six coordination complexes were successfully synthesis through self-assembly of multiple components. Here upon ligands and different carboxylates variation, we reported on the assembly of six new organic–inorganic hybrid complexes with different silver nuclei. Four novel complexes based pza ligand and two new complexes based pzn ligand, namely {Ag6(pza)(pca)3(H2O)}n (1), {Ag2(pza)(pda)(H2O)}n (2), {Ag(pza)(pma)1/2⋅2H2O}n (3), {Ag2(pza)(pna)⋅3H2O}n (4), {Ag(pza)(pna)1/2}n (5), {Ag(pza)(pma)1/2⋅2H2O}n (6) have been synthesized successfully. A novel process for the synthesis of complexes 5 and 6 was pzn ligand with in situ reaction in solution to be pza in the formation of crystals. They were fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Complexes 1–3 and 5 show 2D layer structures and complexes 4 and 6 are 1D chain structures which is depicted in Scheme 1 . A noticeable structure feature in complex 1 is that the arrangement of Ag(I) ions is a 2D sheet. And the pca ligands anchor on the 2D silver net to form 2D layer structure. In complex 3 is 1D infinite chain structure which contains 1D silver chain.

Three Ag(I) coordination complexes (CCs), namely {Ag 2 (epyz)(npt)} n ( 1 ), {Ag 2 (tpyz)(npt)} n ( 2 ), {Ag 2 (npt)(NH 3 ) 2 } n ( 3 ), [epyz = 2-ethyl-3-methylpyrazine, H 2 npt = 3-nitro-1,2-benzenedicarboxylic acid, tpyz = 2,3,5-trimethylpyrazine, mpyz = 2,3,5,6-tetramethylpyrazine] have been synthesized by solution phase ultrasonic reactions of Ag 2 O with H 2 npt and various pyrazine derivatives ligands under the ammoniacal condition. All the complexes have been characterized by X-ray diffraction, elemental analyses and IR spectra. Complexes 1 and 2 show two-dimensional network. Compound 3 exhibits 1D-chain structure. However, complex 3 shows 3D supramolecular structure results from the linkage of neighboring layers through a rich hydrogen-bonding system involving the ammonia molecules with carboxyl oxygen atoms and the nitro oxygen atoms. Zigzag Ag 4 subunits (SBUs) were observed in compounds 1 and 3, while the complex 2 only shows Ag2⋯Ag2 interactions. The structural diversity of the compounds indicated the Ag⋯Ag argentophilicity, the coordination modes of carboxyl groups and the difference pyrazine derivatives play an important role in the formation of such coordination architectures. The thermogravimetric analyses and photoluminescence of the complexes were also investigated.

To systematically explore the influence of pyridazine ligands and aromatic polycarboxylate on the existence of argentophilicity, four inorganic–organic hybrid Ag(I) complexes were obtained by one-pot ultrasonic reaction. Four complexes were named [Ag 6 (pdz) 2 (btc) 2 ] n ( 1 ), [Ag 2 (pdz)(npt)] n ( 2 ), [Ag 2 (pdz)(pma) 1/2 ] n ( 3 ), and [Ag 2 (pdz)(npa)·H 2 O] n ( 4 ) (pdz = pyridazine, H 3 btc = 1,3,5-benzene tricarboxylic, H 2 npt = 3-nitrophthalic acid, H 4 pma = pyromellitic acid, H 2 npa = 1,4-naphthalenedicarboxylic acid). Structural analyses reveal that complexes 1 – 4 display diverse 2D or 3D frameworks, which all of the N-donor pdz ligands exhibit the same coordination mode but the distances of the silver atoms which link to the pdz ligands are different to each other. Complex 1 shows Ag 6 clusters and the cluster is comprised by two distorted tetrahedron silver units. And the clusters are shared by two silver ions to form 1D silver chains. Complex 2 features 1D silver chains which are formed by the Ag 4 units and the four Ag(I) ions are in the vertices of parallelogram. Complex 3 is an interpenetrating architecture with the pdz ligands alternately repeating up and down in ac plane. The structure of complex 4 is a 2D layer structure which the pdz and npt ligands alternately repeat along a axis. Moreover, complexes 1 – 4 indicate different photoluminescence behaviors in the solid state.

Two novel [Ag 2 pyd] n ( 1 ) and [Ag 4 (apyz) 3 (pyd) 2 ·3H 2 O] n ( 2 ) supramolecular frameworks constructed by H 2 pyd (2,3-pyridinedicarboxylic acid) were synthesized and characterized by X-ray single crystal diffraction, elemental analyses and IR spectra. The pyd building block was extended into well-ordered supramolecular frameworks by Ag O and Ag···Ag interaction. Ligand-supported weak argentophilic interactions are observed in compounds 1 and 2 , but novel 1D Ag···Ag silver-wire structure is only in 1 . The linkers of pyd and apyz (aminopyrazine) play an important role in the self-assembly process. The combination of pyd ligands and Ag ions generate a 2D layer structure in complex 1 and pyd ligands adopt different coordination modes to connect Ag atoms to form 3D supramolecular framework in complex 2 . Comparing the experimental results, it is clear that the apyz ligand plays a crucial role in the formation of the resulting structures. The results are reported in this article.

Two new metal–organic framework namely, [ Ag 3 ( dmpyz ) 1.5 ( btc ) ] n (1), and [ Ag 2 ( dmpyz ) ( pta ) ] n (2), have been synthesized and structurally characterized. Compound 1 is a 3D structure incorporating μ 5 - ( η 1 , η 1 ) : ( η 1 , η 1 ) : ( η 1 , η 1 ) btc and μ 2 - N 1 , N 1 , μ 2 - N 2 , N 3 dmpyz ligands. In compound 2, the μ 5 - η 1 : η 2 : η 3 : η 1 pta and the dmpyz ligands link the [ Ag 4 O 2 ] units into a 2D structure. It is noteworthy that the Ag⋯Ag interactions were observed in the two coordination polymers. The results show that the structural diversity of the polymers is mainly attributed to the usage of diverse ancillary carboxylate ligands. The thermal stabilities and photoluminescence behaviors were addressed.

Four silver(I) coordination polymers (CPs), namely, [Ag2(mpyz)(ipa)]n (1) [Ag3(mpyz)(btc)]n (2) [Ag4(apyz)2(ipa)·0.5 DMF]n (3) [Ag3(apyz)2(btc)]n (4), have been purposefully synthesized under ultrasonic treatment of methylpyrazine (mpyz), aminopyrazine (apyz), isophthalic acid (H2ipa), 1,3,5-benzenetricarboxylic acid (H3btc) and AgNO3. And they were characterized by elemental analysis and X-ray single-crystal diffraction. Complexes 1 and 2 based on the same auxiliary ligand mpyz show various structures with silver chain. Complex 1 features a three-dimensional (3D) structure which consists of 1D helical silver chains. Complex 2 possesses an infinite silver chain with repeated Ag-triangle units. Complexes 3 and 4 with apyz as auxiliary ligand exhibit different structures. Complex 3 exhibits a 2D 44-sql network with the 1D double chains and complex 4 shows Ag6 units which are connected by Ag⋯Ag interaction in the 3D coordination network. Effects of the aromatic polycarboxylates on the structures and the intricacy of the self-assembly process were discussed. Additionally, results about infrared spectroscopy (IR), thermogravimetric analyses (TGA) and photoluminescence spectra behaviours of the compounds were also discussed.

Two mixed-ligand silver(I) coordination complexes (CCs), [Ag 4 (mpyz)(npt) 2 ·(H 2 O) 2 ] n ( 1 ) and [Ag 4 (mpyz) (npt) 2 ] n ( 2 ) were synthesized with reactions of methyl-pyrazine(mpyz) and 3-nitro-1,2-benzenedicarboxylic acid (H 2 npt) with silver nitrate in different solvent systems and were structurally characterized by single-crystal X-ray crystallography. Structural differences of CCs are due to the effects of solvent systems and the intricacy of the self-assembly process for these systems. For 1 , the Ag 4 unit which is like Y letter which stand upside and down and repeat to form a 1D-6 3 -silver-ring which shares Ag1 and Ag2 only with npt ligands. The eight Ag ions of complex 2 are in a shape like the branches of a tree which repeat to form a 1D silver chain. Effects of solvents on the structures, as well as the intricacy of the self-assembly process were discussed. The photoluminescence, infrared spectroscopy (IR) and thermogravimetric analyses (TGA) behaviors of the compounds were also discussed.

Four 3D POM-based silver coordination polymers, namely, [Ag17(ptz)11(PW12O40)2]n (1), [Ag17(ptz)11(PMo12O40)2]n (2), [Ag12(ptz)6(CN)2(SiW12O40)]n (3), and [Ag19(ptz)8(H2ptz)(H3ptz)(AgP5W30O110)·7H2O]n (4), have been obtained by solvothermal reaction of AgNO3 and 5-phenyl-1H-tetrazole (Hptz) ligand in the presence of four types of polyoxometalates. Structural analysis shows that four types of Ag(I)···π interactions, m-η(1), m/p-η(2), o/m-η(2), and o/m/p-η(3), were observed in compounds 1-4, depending on the polyoxometalates used. The in situ generated CN(-) ion in compound 3 shows unprecedented mixed σ and π bonding modes, similar to the C2(2-) ion in well-studied silver acetylides. For 4, the Na(+) ion in the Preyssler heteropolyoxoanion, [NaP5W30O110](14-), was exchanged by Ag(I) under solvothermal conditions, generating a novel [AgP5W30O110](14-) anion. In addition, the photoluminescence behavior of 1-4 was also investigated.

Two heterometallic cage-like Dy24M2 (M = Ni, Mn) cluster compounds have been synthesized through self-assembly of the metal ions and the myo-inositol ligand templated by three ClO4− anions.

Two one-dimensional acetate chains, GdIII–MnII (1) and GdIII–CoII (2), have been prepared. Magnetic investigations indicate that the magnetic entropy changes in 1 and 2 are up to 38.70 and 35.18 J kg−1 K−1 at ΔH = 7 T, and 31.08 and 28.67 J kg−1 K−1 at ΔH = 3 T, respectively.

A tripodal amide based ligand, tris-{(2-carbamoyl-5-carbomethoxy-pyridine)-2-ethyl}amine (H3L, 1), was synthesized and structurally characterized by single crystal X-ray diffraction. Investigation of the cation recognition behavior showed that the ligand has selective colorimetric sensing properties for cobalt(II) ions by an obvious color change from colorless to yellow. To investigate the sensing mechanism of H3L for Co(2+) ions, UV-vis absorption spectroscopy and single-crystal structural analysis were performed. The mixture of the ligand and cobalt(II) ions displayed selective colorimetric sensing properties for weak acid anions, such as CO3(2-), Ac(-), HCO3(-), SO3(2-), and PO4(3-). Detailed (1)H NMR experiments revealed that the basicity of the anions played an important role in the intensity of the interaction between the ligand and anions. The structures of compounds CoL (2), Co-Ac-HL (3), H4L-NO3 (4), and H4L-ClO4 (5) were also determined by single crystal diffraction studies.

The ultrasonic reactions of Ag2O with 1, 4-bis(imidazol-1-ylmethyl) benzene (bix) and ancillary carboxylate ligands under the ammoniacal condition lead to two new coordination compounds, namely [Ag4(bix)4(pma)·(H2O)18]n(1) and [Ag(bix)(onb)·H2O]n(2)(H4pma = pyromellitic acid, Honb = o-nitrobenzoic acid). Both of the complexes have been characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. In complex 1, the Ag-bix 1D chains are connected with the 2D nets containing [Ag4(bix)2(pma)2] to form a 3D framework by Ag⋯Ag interaction. In complex 2, the coordination bonds link Ag(I) ions and bix ligands to form 1D chains which are extended into a 2D layer by inter-chain hydrogen bonds. The Ag⋯Ag interaction is also observed in 2. Moreover, the photoluminescence properties of the complexes were also investigated in the solid state at room temperature.

Four 3D coordination polymers, [Co7(OH)4(H2O)2(ina)4(ip)3]·10H2O (1·10H2O, ina = isonicotinate, ip = isophthalate), [Ni7(OH)4(H2O)2(ina)4(ip)3]·10H2O (2·10H2O), [Co7(OH)4(H2O)2(ina)4(pip)3]·5H2O (3·5H2O, pip = 5-phenyl-isophthalate), and [Ni7(OH)4(H2O)2(ina)4(pip)3]·5H2O (4·5H2O), respectively, were hydrothermally synthesized. They crystallized in the orthorhombic space group Pba2 for 1·10H2O and 2·10H2O and monoclinic space group P2/n for 3·5H2O and 4·5H2O, respectively, and were constructed with the identical 8-connected heptanuclear {M7(OH)4} (M = Co(II) or Ni(II)) clusters, possessing uninodal hexagonal primitive net with the point symbol {3(6)·4(18)·5(3)·6}. The four coordination polymers showed dominant antiferromangetic properties, in which 1·10H2O shows spin-canted behavior and 2·10H2O exhibits the coexistence of spin canting and spin glass. Meanwhile, the activated polymers 1 and 2 possessed permanent porosity, displaying relatively large H2 uptake capacity (77 K, 1 atm) of 114 and 133 cm(3) g(-1), and CO2 uptake capacity (273 K, 1 atm) of 65.8 and 73.3 cm(3) g(-1), for 1 and 2, respectively.

Four Zn(II) coordination complexes, namely {[Zn(pmbm) 2 (tpa)]·H 2 O} n (1), {[Zn(pmbm)(phda)]·2(H 2 O)} n (2), [Zn(pmbm)(aze)] n (3), {[Zn(pmbm)(1,4-ndc)]·2(CH 3 OH)} n (4) [pmbm = 1-(4-pyridylmethyl)-benzimidazole, H 2 tpa = terephthalic acid, H 2 phda = phenylenediacetic acid, H 2 aze = azelaic acid, 1,4-ndcH 2 = 1,4-naphthalenedicarboxylic acid] have been synthesized by solution phase ultrasonic reactions of Zn(AC) 2 ·2H 2 O with pmbm and various dicarboxylates ligands under the ammoniacal condition. All the complexes have been characterized by elemental analyses, IR spectra and X-ray diffraction. Complexes 1 and 2 exhibit one-dimensional chains structure and complex 3 and 4 are two-dimensional sheets structure with (4,4) topology. Complexes 1 – 4 spanning from one-dimensional chains to two-dimensional sheets suggest that dicarboxylates play significant roles in the formation of such coordination architectures. The photoluminescences of the complexes were also investigated in the solid state at room temperature.

Herein, twenty-seven coordination polymers were synthesised using Mn2+, Co2+, Ni2+, Cu2+ and Zn2+ in organic solvents. Structural analyses show that metal ions are the most important factor that influences coordination polymer assembly. Metal ions determine the type of metal centre and structural topology. The organic ligand benzene dicarboxylic acid is the second most influential factor. Synthetic conditions are not key factors in this research system.

National Natural Science Foundation of China (NSFC) [90922012, 20971106, 21021061, 21271091]; Natural Science Foundation of the Jiangsu Higher Education Institutions [11KJA430009]; PAPD of Jiangsu Higher Education Institutions

NNSFC [20901064, 20825103, 21021061, 21071119, 90922031]; Foundation for the Author of National Excellent Doctoral Dissertation of China [201219]; Ministry of Science and Technology of China [2012CB821704]

Dielectric anisotropy of anilinium perchlorate is investigated at various temperatures. Crystal structures at different temperatures reveal that significant dielectric change between low and high dielectric states is closely related to the disorder of the anilinium cation and perchlorate anion at high dielectric state; meanwhile, the conductivity after phase transition also contributes a lot to the high dielectric state.

Twelve coordination compounds of Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+, with mixed organic ligands 5-methylisophthalic acid, 2,2′-bipyridine or phenanthroline, have been hydrothermally synthesised and characterised. The magnetic properties of the Mn2+, Co2+, Ni2+ and Cu2+ compounds have been investigated. Structure analysis shows that the assemblies with a bridging ligand possessing a smaller methyl group (compared to the tert-butyl group) afford coordination compounds containing multinuclear metal centres and structures of higher dimension. The result shows that the structures and properties of the metal–organic materials can be finely tuned by the substituent on the organic bridging ligands.

Two monoxides of typical smaller chlorofullerenes, (#271)C50Cl10O and (#913)C56Cl10O, featured with double-fused-pentagons, were synthesized to demonstrate further regioselective functionalization of non-IPR (IPR = isolated pentagon rule) chlorofullerenes. Both non-IPR chlorofullerene oxides exhibit an epoxy structure at the ortho-site of fused pentagons. In terms of the geometrical analysis and theoretical calculations, the principles for regioselective epoxy oxidation of non-IPR chlorofullerenes are revealed to follow both "fused-pentagon ortho-site" and "olefinic bond" rules, which are valuable for prediction of oxidation of non-IPR chlorofullerenes.

Removal of vapor-phase elemental mercury (Hg0) over an activated coke (AC) and activated coke supported CuO catalyst (CuO/AC) were studied under N2+HCl atmosphere. This paper describes the influences of CuO loading, reaction temperature, Hg0 concentration and space velocity on Hg0 removal over CuO/AC. It was found that CuO/AC had a higher Hg0 removal capability than that of AC, which can be attributed to the oxidation activity of CuO. The capability of CuO/AC for Hg0 removal increased with an increase of CuO loading (1-20 wt.%). The Hg0 removal capability was the highest at around 180 °C in the temperature range of 120-200 °C, which can be due to the co-effect of adsorption and oxidation. As Hg0 concentration and space velocity decreased, the Hg0 removal efficiency increased.

National Natural Science Foundation of China (NSF of China) [90922012, 20971106, 21021061]; Specialized Research Fund for the Doctoral Program of Higher Education [20110121110012]

Two metal-organic frameworks constructed from nanosized Cu(20) and Cu(30) wheels have been obtained under hydrothermal conditions based on 1,2,3-triazole and 1-H-1,2,3-benzotriazole, respectively. Crystal structure analysis shows that their differences in the size and nuclearity of Cu(20) and Cu(30) wheels are attributed to the steric effect of ligands.

Composite oxides materials CuSnO3as anode materials for lithium-ion batteries were synthesized by chemical coprecipitation method using SnCl4•5H2O, NH3•H2O and Cu(NO3)2•3H2O as raw materials.The precursor CuSn(OH)6and CuSnO3powders were characterized by thermogravimertric(TG) analysis and differential thermal analysis(DTA), X-ray diffraction(XRD), and transmission electron microscope (TEM). The electrochemical properties of CuSnO3powders as anode materials of lithium ion batteries were investigated comparatively by galvanostatic charge-discharge experiments. The results show the average particle size of amorphous CuSnO3is 70nm. The initial capacity during the first lithium insertion is 1078 mA•h/g and the reversible charge capacity in first cycle is 775 mA•h/g. After 20 cycles, the charge capacity is 640 mA•h/g and this material shows moderate capacity fading with cycling. As a novel anode material for lithium ion batteries, amorphous CuSnO3demonstrates a large capacity and a low insertion potential with respect to Li metal.

通讯作者地址: Huang, RB (通讯作者),Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 2. Xiamen Univ, Coll Chem & Chem Engn, Dept Chem, Xiamen 361005, Peoples R China 电子邮件地址: rbhuang@xmu.edu.cn

通讯作者地址: Sun, D (通讯作者),Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China 地址: 1. Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Fujian, Peoples R China 电子邮件地址: dsun@sdu.edu.cn; rbhuang@xmu.edu.cn

通讯作者地址: Sun, D (通讯作者),Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China 地址: 1. Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 电子邮件地址: dsun@sdu.edu.cn; rbhuang@xmu.edu.cn

National Natural Science Foundation of China [20721001]; MSTC [2007CB815301]; Independent Innovation Foundation of Shandong University [2011GN030]; Special Fund for Postdoctoral Innovation Program of Shandong Province [201101007]

A pentanuclear dysprosium cluster, [Dy(5)(μ(3)-OH)(6)(Acc)(6)(H(2)O)(10)]·Cl(9)·24H(2)O (1), has been synthesized through the reaction of 1-amino-cyclohexanel-carboxylic acid (Acc) and DyCl(3)·5H(2)O. Crystal structural analysis reveals that the metal core of cluster 1 shows an unprecedented trigonal bipyramidal (TBP) geometry. Magnetic studies indicate that the Dy(5) cluster exhibits slow magnetic relaxation.

A novel silver(I) wire sustained by 4-tert-butylbenzoate and ligand-unsupported Ag⋯Ag interactions, [Ag3(tbb)3(NH3)2]n (1, Htbb = 4-tert-butylbenzoic acid), has been synthesized and structurally characterized. In 1, three tbb ligands bind three Ag(I) ions to form a trinuclear subunit through ligand-supported Ag⋯Ag interactions. The inversion-related subunits are further extended to an infinite 1D zigzag Ag(I) wire through the ligand-unsupported Ag⋯Ag interactions. Argentophilicity (3.0283(14)–3.0910(17) A) plays an important role in determining the infinite silver(I) wire. The thermal stability and luminescent behavior of 1 were also discussed.

18 coordination compounds of Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+, with mixed organic ligands 5-tert-butylisophthalic acid, 2,2′-bipyridine or phenanthroline, have been hydrothermally synthesized and characterized. Structure analysis shows that the ionic radius of a metal ion determines the form of the metal centre and the structure of the product. Large metal ions tend to have higher coordination numbers, connect to more bridging ligands and form multinuclear metal centres. On the contrary, small metal ions tend to connect to fewer bridging ligands, and act as mononuclear metal centres for discrete coordination compounds or low dimensional coordination polymers. The influences of other factors such as molar ratio of reactants, pH and temperature, have also been discussed. The magnetic properties of the temperature dependent cobalt compounds have been investigated.

An unprecedented (ethanol)4 cluster is observed in a photoluminescent silver(I) coordination polymer host, [Ag2(dmt)2(nda)·2EtOH]n (1, dmt = 2,4-diamino-6-methyl-1,3,5-triazine, H2nda = naphthalene-1,4-dicarboxylic acid, EtOH = ethanol). In 1, two pairs of symmetry-related ethanol molecules are hydrogen bonded with each other by O H⋯O hydrogen bonds to form a R44(8) hydrogen bond motif where all the ethanol molecules are proton acceptor and proton donor at the same time. The thermal stability and luminescent behavior of 1 were also discussed.

Three new silver(I) coordination polymers (CPs) [Ag 4 ( o -mba) 4 ] n ( 1 ), [Ag 2 ( m -mba) 2 ] n ( 2 ) and [Ag 2 ( p -mba) 2 ] n ( 3 ) have been constructed from AgNO 3 and three isomeric ligands, o -, m -, p -methylbenzoic acid (Hmba = methylbenzoic acid), and characterized by elemental analysis, infrared (IR) spectroscopy, powder X-ray diffraction (PXRD), and single crystal X-ray diffraction. In 1 , μ 3 – η 1 : η 2 and μ 4 – η 1 : η 3 o -mba ligands link Ag(I) ions to form a 1D chain based on a tetranuclear Ag(I) aggregation with a folded rhombus geometry. When the methyl group was moved from o - to m -position, we obtained 2 as a similar 1D chain but incorporating a parallelogram tetranuclear Ag(I) aggregation, where two crystallographically independent m -mba ligands show the identical μ 3 – η 1 : η 2 coordination fashion. Using p -Hmba as ligand, complex 3 becomes a 2D (3,6) net with μ 3 – η 1 : η 2 p -mba ligands. Interestingly, all CPs exhibit diverse Ag⋯Ag and Ag⋯C interactions, which are in the range of 2.7899(10)–3.3666(7) A and 2.843(11)–3.336(10) A, respectively. These secondary interactions cooperatively play important roles in the formation of the resulting 3D supramolecular frameworks. The structural dissimilarity can be mainly assigned to the change of relative positions of methyl and carboxyl groups. Moreover, the thermal stabilities and photoluminescence properties of 1 – 3 were investigated.