Inorganic Chemistry Communications (v.12, #6)

Contents List (iii-xiii).

The hydrothermal reaction of CdII, H2L and bpp leads to the generation of a new helical coordination polymer, [Cd2L2(bpp)2] n (1). At room temperature, the complex shows strong fluorescent emission bands in the solid state (H2L = 1,3-adamantanediacetic acid, bpp = 1,3-di-4-pyridylpropane).A novel cadmium coordination polymer [Cd2L2(bpp)2] n (1) (H2L = 1,3-adamantanediacetic acid and bpp = 1,3-di-4-pyridylpropane) was prepared under hydrothermal condition. The three-dimensional (3D) structure is built from the interlinking lamellars. The CdII ions are six- and seven-coordinated and linked by L2− ligands, which results in the right- and left-handed helical chains. The layers are stacked with each other via bpp to generate a 3D architecture. At room temperature, the complex 1 shows the strong fluorescent emission bands in the solid state.
Keywords: Helical coordination polymer; Hydrothermal synthesis; Crystal structure; Luminescent property;

An unprecedented 2-D organic–inorganic hybrid sandwich-type polyoxotungstate containing O-donor organic ligands [DMAH]4{[Mn(DMF)4]2[Mn4(DMF)2(α-B-HPW9O34)2]} (1) has been solvothermally synthesized and characterized by elemental analysis, IR, UV spectra and X-ray single-crystal diffraction.An unprecedented 2-D organic–inorganic hybrid sandwich-type polyoxotungstate containing O-donor organic ligands [DMAH]4{[Mn(DMF)4]2[Mn4(DMF)2(α-B-HPW9O34)2]} (1) (DMA = dimethylamine, DMF = N,N-dimethylformamide) has been solvothermally synthesized and characterized by IR, UV spectra and X-ray single-crystal diffraction. The 2-D organic–inorganic hybrid network of 1 is built by tetra-MnII substituted sandwich-type polyoxotungstates [Mn4(DMF)2(α-B-HPW9O34)2]8− and [Mn(DMF)4]2+ cation bridges, which displays the common 2-D (4,4) topological net. It should be noted that the major difference between [Mn4(DMF)2(α-B-HPW9O34)2]8− in 1 and the reported [Mn4(H2O)2(α-B-PW9O34)2]10− is that two DMF ligands substitute two H2O ligands on the Mn4O16 unit located in the sandwich belt. Magnetic susceptibility measurement indicates the occurrence of antiferromagnetic coupling interaction within MnII ions.
Keywords: Solvothermal synthesis; Polyoxotungstate; Keggin structure; Polyoxometalate;

Competition between 3d metals(II) and palladium(II) in the reaction of heterobimetallic complexes Pd(μ-OOCMe)4M(OH2) (M = Ni, Co, Mn) with azobenzene by Sergei E. Nefedov; Elena V. Perova; Ilya A. Yakushev; Natalia Yu. Kozitsyna; Michael N. Vargaftik; Ilya I. Moiseev (454-456).
The reaction of PdII(μ-OOCMe)4MII(OH2) (M = Ni, Co, Mn) with azobenzene under mild conditions produces the homonuclear complex with ortho-metallated azobenzene (PhN = NC6H4)2Pd2(μ-OOCMe)2 (4) in higher than 90% yield as the sole Pd-containing reaction product, while the co-metals are recovered as the corresponding MII acetates.The reaction of PdII(μ-OOCMe)4MII(OH2) (M = Ni, Co, Mn) with azobenzene under mild conditions produces the homonuclear complex with ortho-metallated azobenzene (PhN = NC6H4)2Pd2(μ-OOCMe)2 (4) in higher than 90 % yield as the sole Pd-containing reaction product, while the co-metals are recovered as the corresponding MII acetates.
Keywords: Heterobimetallic paddlewheel complexes; Palladium; Azobenzene; Ortho-metallation; X-ray structure;

Discrete M2L2 metallacycle and M2L4 cage frameworks and anion competitive reactions of Cu2L4 type receptor by Hong-Ke Liu; Ying Cai; Wenping Luo; Fengyu Tong; Chunxiang You; Shenghong Lü; Xiaohua Huang; Heng-Yun Ye; Fu Su; Xiujian Wang (457-460).
The structures of a Cu2L2 rectangle and Cu2L4 cage complexes were reported and anion competitive reactions showed that the anion selective order is ClO 4 - > BF 4 - > NO 3 - > Cl - , and ClO 4 - is the biggest and most preferable one, so far. This M2L4 cage receptor could selectively “recognize” anions of different size and shape in the solid state.Complexes [Cu2(bitmb)2Cl4] (1), [ ( CH 3 OH ) ( NO 3 ) ⊂ Cu 2 ( bitmb ) 4 ] ( NO 3 ) 3  · CH3OH · 6 H2O (2) and [ BF 4 ⊂ Cu 2 ( bitmb ) 4 ] (BF4)3  · 2 CH3OH · 4 H2O (3) are obtained by reaction of bitmb and Cu2+ salts with different anions ( BF 4 - , NO 3 - or Cl - ) at different M:L ratio (1:1, 1:2 or 1:2). The results reveal that complex 1 is a neutral Cu2L2 rectangle and complexes 2 and 3 are M2L4 cage-like frameworks with an anion as guest. The anion competitive reaction of the Cu2L4 type receptor with tetrahedral, triangular and spherical anions ( ClO 4 - , BF 4 - , NO 3 - and Cl - ) is reported. The anion competitive experiments demonstrate that the anion selective order is ClO 4 - > BF 4 - > NO 3 - > Cl - , and ClO 4 - is the biggest and most preferable one, so far.
Keywords: Anion receptor; M2L4 Cage compounds; Anion competitive reaction; Tetrahedral; Triangular and spherical anions; Hydrogen bonds and π⋯π interactions;

Assembly, crystal structure and luminescent properties of coordination polymer of europium nitrate with an amide type bridging podand by Dian-Yi Liu; Zhuo-Qun Kou; Ya-Fei Li; Kuan-Zhen Tang; Yu Tang; Wei-Sheng Liu; Min-Yu Tan (461-464).
A novel one-dimensional coordination polymeric structure comprised of dinuclear metallorings connected by ligands has been rationally assembled by the reaction of europium nitrate and an amide type bridging podand, 1,3-bis{[(2′-benzylaminoformyl)phenoxyl]methyl}benzene. Under the excitation, the complex exhibited characteristic emissions of europium ion and could be significant in the field of supramolecular photonic devices.A novel one-dimensional coordination polymeric structure comprised of dinuclear metallorings connected by ligands has been rationally assembled by the reaction of europium nitrate and an amide type bridging podand, 1,3-bis{[(2′-benzylaminoformyl)phenoxyl]methyl}benzene (L). At the same time, the luminescent properties of the Eu(III) complex were also investigated. Under the UV excitation, the complex exhibited characteristic emissions of europium ion and could be significant in the field of supramolecular photonic devices. The triplet excited state T1 of the ligand is well placed to allow energy transfer to Eu3+ excited states.
Keywords: Coordination polymer; Europium nitrate; Bridging podand; Luminescent properties;

Self-assembly of 4,4′-bipyridylethylene bidentate ligand with the dinuclear arene ruthenium clip [Ru26-p-cymene)2(μ-oxalato)Cl2] affords the cationic organometallic rectangle [Ru46-p-cymene)4(μ-oxalato)2(μ-bpe)2]4+. Upon UV irradiation, dimerisation of the two olefinic double bonds of the bpe ligands occurs, thus giving rise to the cyclobutane derivative [Ru46-p-cymene)4(μ-oxalato)2(μ-tpcb)]4+. The molecular structure of these two systems was deduced by one-dimensional and two-dimensional NMR experiments.Self-assembly of 4,4′-bipyridylethylene (bpe) bidentate connector with the dinuclear arene ruthenium clip [Ru26-p-cymene)2(μ-oxalato)Cl2] in the presence of silver triflate affords the cationic organometallic rectangle [Ru46-p-cymene)4(μ-oxalato)2(μ-bpe)2]4+ ([1][CF3SO3]4). Upon UV irradiation of a methanol solution of [1]4+, dimerisation of the olefinic double bonds of the two parallel bpe ligands occurs, thus giving rise to the [2+2] cycloaddition derivative [Ru46-p-cymene)4(μ-oxalato)2(μ-tpcb)]4+ ([2][CF3SO3]4) (tpcb = tetrakis(4-pyridyl)cyclobutane). The [2+2] photodimerisation reaction was followed by 1H NMR spectroscopy. Moreover, the molecular structure of these two systems was deduced by one-dimensional and two-dimensional NMR experiments (1H, 13C, ROESY, COSY, HSQC). These data suggest the formation of only the rctt-tetrakis(4-pyridyl)cyclobutane isomer.
Keywords: Bridging ligands; Arene ligands; Ruthenium; Supramolecular chemistry; [2+2] Cycloaddition;

Novel hetero-polynuclear metal complexes (CuL)3[Mn(NCS)5]2 and (NiL)3[Mn(NCS)5]2 containing trigonal bipyramidal geometric [Mn(NCS)5]3− as bridging ligand by Ying-Ping Quan; Ping Yin; Nan-Nan Han; Ai-Hong Yang; Hong-Ling Gao; Jian-Zhong Cui; Wei Shi; Peng Cheng (469-472).
The thiocyanate-bridged pentanuclear (CuL)3[Mn(NCS)5]2 (1) and (NiL)3[Mn(NCS)5]2 (2) are isomorphic, and Mn(II) is coordinated by five N atoms from five thiocyanate ligands in a trigonal bipyramidal geometry, which is a novel coordination mode and observed in the complexes for the first time.Two thiocyanate-bridged hetero-pentanuclear complexes (CuL)3[Mn(NCS)5]2 (1) and (NiL)3[Mn(NCS)5]2 (2) have been successfully synthesized and characterized by X-ray single crystal diffraction, elemental analysis, IR, TGA and magnetic measurements. (L = N-dl-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene). Single crystal structure analysis indicates that complex 1 and 2 have similar structures in which the Mn(II) atom is five-coordinated in a trigonal bipyramidal geometry by five N atoms from five thiocyanate ligands. The Cu(II) and Ni(II) both show two different coordination environments, square pyramidal and distorted octahedron. Three Cu(II) (or Ni(II)) ions and two Mn(II) ions are bridged by the end-to-end thiocyanate ligands to form pentanuclear entities. The pentanuclear entities are further linked to 3D framework by the hydrogen bonds. The variable-temperature magnetic measurements for 1 indicated weak antiferromagnetic interaction between the Cu(II) and Mn(II) ions.
Keywords: Copper; Nickel; Trigonal bipyramidal coordinated manganese; Thiocyanate; Tetraazamacrocyclic ligand; Magnetic properties;

Direct synthesis of Co/Mn complex with Co-semisepulchrate entity by Asya O. Beznischenko; Valeriya G. Makhankova; Vladimir N. Kokozay; Viktoriya V. Dyakonenko; Oleg V. Shishkin (473-475).
A novel compound [CoL][Mn(ox)2]Cl·3H2O [L – N(CH2NHC2H4NH2)3, tris(((aminoethyl)amino)methyl)amine] (1), has been synthesized and structurally characterized. The compound 1 represents a rare example constructed by 1D polymeric [ Mn ( ox ) 2 ] n 2 n - anions and [CoIIIL]3+ semisepulchrate-type cations. The advantages of the procedure elaborated include: one pot reaction, good efficiency and easily available starting materials.A novel compound [CoL][Mn(ox)2]Cl·3H2O [L – N(CH2NHC2H4NH2)3, tris(((aminoethyl)amino)methyl)amine] (1), has been synthesized and structurally characterized. The compound 1 represents a new and rare example constructed by 1D polymeric [ Mn ( ox ) 2 ] n 2 n - anions and semisepulchrate [CoIIIL]3+ cations. An efficient and simple procedure for the synthesis of 1 has been proposed. The advantages of this procedure include: one pot reaction, good efficiency and easily available starting materials.
Keywords: Direct synthesis; Cobalt; Semisepulchrate; In situ reaction;

A mononuclear mixed ligand complex of iron-Schiff base has been synthesized and characterized by elemental analysis, spectral studies and X-ray crystallography. This complex was found as an efficient catalyst for highly selective oxidation (95–100%) of various sulfides to corresponding sulfoxides by urea hydrogen peroxide (UHP) under mild conditions.A mononuclear mixed ligand complex of iron, [FeIII(N-OPh-sal)(acac)EtOH], where Hacac and N-HOPh-Hsal denote acetylacetone and N-hydroxyphenyl-salicylideneamine, respectively, has been synthesized and characterized by elemental analysis, spectral studies and X-ray crystallography. The catalytic system containing this complex and urea hydrogen peroxide as oxidizing agent was used to selectively oxidize a range of sulfides to the corresponding sulfoxides in good yields under mild conditions. The electronic spectra of the catalytic system were applied to explore reactivity and stability of the catalyst during sulfide oxidation reactions and to examine the nature of active species, as well.
Keywords: Iron(III) complex; Tridentate Schiff base; Mixed-ligand; Urea hydrogen peroxide; Catalytic oxidation; Sulfide;

A zinc coordination polymer, [ZnI2{Ph2P(O)-CH2CH2-P(O)Ph2}] n (1), has been prepared, which features a one-dimensional concavo-convex chain with alternative ZnI2 and 1,2-bis(diphenylphosphino)ethane dioxide (dppeO2) moieties. The dppeO2 ligand adopts the bridging coordination mode between two zinc atoms.A zinc coordination polymer, [ZnI2{Ph2P(O)-CH2CH2-P(O)Ph2}] n (1), has been prepared, which features a one-dimensional concavo-convex chain with alternative ZnI2 and 1,2-bis(diphenylphosphino)ethane dioxide (dppeO2) moieties. The dppeO2 ligand adopts the bridging coordination mode between two zinc atoms.
Keywords: Coordination polymer; Crystal structure; Zinc(II); 1,2-Bis(diphenylphosphino)ethane dioxide;

Decomposition of allantoin in the presence of Cu(II) ions resulting in the formation of a coordination polymer containing oxalate species by Mariola Puszyńska-Tuszkanow; Marek Daszkiewicz; Gabriela Maciejewska; Maria Cieslak-Golonka (484-486).
The reaction of Cu(II) nitrate dihydrate solution with allantoin in DMSO/water solution led to the formation of oxalate ion. As a result, the novel coordination polymer, {Cu(ox)(DMSO)2] n , was formed.A novel Cu(II) coordination polymer, [Cu(ox)(DMSO)2] n (1) (ox-oxalate dianion, DMSO-dimethyl sulphoxide) has been prepared in the reaction of copper nitrate dihydrate and allantoin (5-ureidohydantoin) in DMSO/water solution. Compound (1) crystallizes in the monoclinic, space group P121/c1 with a  = 5.1785(7), b  = 13.6311(18), c  = 8.5386(12) Å, β  = 107.524(12)°, V  = 574,76(14) Å3, Z  = 4, D cal  = 1779 mg/m3, R 1  = 0.0449. The metal ion coordinates through four oxygen atoms belonging to two bidentate bridging oxalate ligands, and two oxygen atoms from two DMSO ligands forming an elongated octahedron. The crystal structure was confirmed by FT-IR and Uv–vis spectroscopic data.
Keywords: Allantoin; Copper; Oxalic acid; Crystal structure; IR spectrum; Electronic spectrum;

A 3D AgCN coordination polymer [(AgCN)3(2-tptz)] n (1) has been isolated from the reaction of AgCN with 2-tptz (2-tptz = 2,4,6-tri(2-pyridyl)-1,3,5-triazin) under solvothermal condition. It was characterized by infrared spectroscopy, elemental analysis and X-ray single-crystal analysis. The structure of 1 features an unprecedented 2D wavelike [AgCN] n substructure and a (3 · 8 · 9)(4 · 8 · 9)(3 · 4 · 8 · 93)(3 · 8 · 92  · 102) topological network which has not been encountered among the reported (3, 4)-connected nets when silver⋯sliver interactions are taken into consideration. Besides, the photoluminescent property of 1 was also investigated.The solvothermal reaction of AgCN with 2-tptz (2-tptz = 2,4,6-tri(2-pyridyl)-1,3,5-triazin) afforded a 3D coordination polymer [(AgCN)3(2-tptz)] n (1). It was characterized by infrared spectroscopy, elemental analysis and X-ray single-crystal analysis. The structure of this polymer features a 2D wavelike [AgCN] n substructure constructed from 18-membered of Ag6(CN)6 rings and 22-membered of Ag8(CN)6C2 rings. When silver⋯sliver interactions are taken into account, the structure of 1 exhibits a (3 · 8 · 9)(4 · 8 · 9)(3 · 4 · 8 · 93)(3 · 8 · 92  · 102) topological network which has not been reported for the (3, 4)-connected nets. The photoluminescent property of the present coordination polymer was also investigated.
Keywords: Coordination polymer; Solvothermal synthesis; Cyanide-bridging; Topology analysis; Luminescent property;

Square-planar d 8 metal pushpull dithiolene complexes: Synthesis and characterization of [Pd(Me2pipdt)(dmit)] by Luca Pilia; Flavia Artizzu; Christophe Faulmann; Maria Laura Mercuri; Angela Serpe; Paola Deplano (490-493).
Experimental and theoretical results on the novel [Pd(Me2pipdt)(dmit)] complex show that an unbalanced electron distribution at the dithiolene core occurs. A solvatochromic absorption tunable with the metal and the ligands suggests that these complexes are promising second-order non-linear chromophoresExperimental and theoretical results on the novel [Pd(Me2pipdt)(dmit)] complex (1) based on the push Me2pipdt (1,4-dimethyl-piperazine-3,2-dithione) and pull dmit (1,3-dithiolo-2-thione-4,5-dithiolato), show that an unbalanced electron distribution at the dithiolene core occurs. The presence of a solvatochromic absorption at low energy, shifted to higher frequency when compared to the corresponding nickel case, points out that these complexes are potential second-order non-linear chromophores, whose properties are tunable with the metal.
Keywords: Pd; Dithiolene; NLO-chromophore; Mixed-ligands; X-ray;

A new Schiff-base type selective fluorescent chemosensor for Cu2+ by Hong-Ge Li; Zheng-Yin Yang; Dong-Dong Qin (494-497).
A new ligand 1-phenyl-3-methyl-5-hydroxypyrazole-4-carbaldhyde(benzoyl) hydrazone was synthesized and studied as ion fluorescent chemosensor, which exhibited high sensitivity and selectivity for Cu2+.An original Schiff-base type fluorescent chemosensor 1-phenyl-3-methyl-5-hydroxypyrazole-4-carbaldehyde(benzoyl)hydrazone (H2L) for Cu2+ has been designed and synthesized. An obvious fluorescence quenching only for Cu2+ demonstrates that ligand H2L exhibits high selectivity and efficient signaling behavior toward micromolar concentration of Cu2+ compared with other metal ions. At the same time, the coordination form between ligand and Cu2+ is elucidated via crystal structure.
Keywords: Schiff-base; Fluorescent chemosensor; Cu2+ complex; Crystal structure;

Two novel coordination polymers, [Zn2(FA)(4,4′-bipy)2]·8H2O (1) and Cd2(FA)(2,2′-bipy) (2), have been synthesized under hydrothermal conditions, and their structures were determined by single-crystal X-ray diffraction. Polymer 1 features an unusual three-dimensional (3D) network with (4.62.83)(42.62.82) topology. Polymer 2 has a complicated 3D framework which displays a strong SHG response and ferroelectric properties.Two novel coordination polymers, [Zn2(FA)(4,4′-bipy)2]·2H2O (1) and Cd2(FA)(2,2′-bipy) (2), (H4FA = 4,4′-(hexafluoroisopropylidene)diphthalic acid, 4,4′-bipy = 4,4′-bipyridine, 2,2′-bipy = 2,2′-bipyridine), have been synthesized under hydrothermal conditions, and their structures were determined by single-crystal X-ray diffraction. Polymer 1 features an unusual three-dimensional (3D) network with (4 · 62  · 83)(42  · 62  · 82) topology. Polymer 2 has a complicated 3D framework and crystallizes in non-centrosymmetric space group (Fdd2) belonging to polar point group (C 2 v ), which displays a strong SHG response and ferroelectric properties. Moreover, the luminescent properties of 1 and 2 have also been investigated.
Keywords: Metal-organic framework; Topology; Luminescence; Ferroelectricity;

Phosphonate supported assembly of nanoscale lotus-leaf-shaped nonanuclear lanthanide clusters by Xinfa Li; Qingyan Liu; Jingxiang Lin; Yafeng Li; Rong Cao (502-505).
Two discrete nonanuclear Ln(III) phosphonate clusters, formulated as [Ln9(OH)(Hpmp)12(ClO4)(H2O)26](ClO4)13  · 18H2O (Ln = Nd for 1 and Pr for 2), have been synthesized and structurally characterized.Two discrete nonanuclear Ln(III) phosphonate clusters, formulated as, [Ln9(OH)(Hpmp)12(ClO4)(H2O)26](ClO4)13  · 18H2O (Ln = Nd for 1 and Pr for 2), were synthesized via the assembly of Ln(ClO4)3 with N-piperidinomethane-1-phosphonic acid (H2pmp) at a pH of 6.2 in aqueous solution. Single crystal X-ray diffraction and powder XRD patterns revealed that they are isostructural. In the crystal structure, the shape of arrangement of the nine Ln(III) ions can be described as a lotus-leaf. Furthermore, temperature-dependent magnetic susceptibilities of 1 and 2 have been investigated.
Keywords: Lanthanide cluster; Lanthanide phosphonate; Zwitterionic phosphonate; Magnetic property;

A red luminescent quadruple stranded dinuclear Eu(III) complex was synthesized shown as below. Bright red LEDs were successfully fabricated by coating the complex onto InGaN chip. The complex may act as a red component in fabrication of white LED with high color-rendering index.A luminescent quadruple stranded dinuclear Eu(III) complex Na2[Eu2(dbt)4] was synthesized, where H2dbt was 2,8-bis(4′,4′,4′-trifluoro-1′,3′-dioxobutyl)-dibenzothiophene. The complex emits the characteristic red luminescence of Eu3+ ion due to the 5 D 0  →  7 FJ (J  = 0–4) transitions under 395 nm-light excitation with a luminescent quantum efficiency of 23%. Bright red light-emitting diodes (LEDs) were fabricated by coating the complex onto 395 nm-emitting InGaN chip. The results indicate that the complex may act as a red component in the fabrication of near UV-based white light-emitting diodes with high color-rendering index.
Keywords: Lanthanide complex; Phosphor; Luminescence; LED;

The first Er(III) homodinuclear complex bridged by 2,2′-bipyrimidine, [Er(tfa)3]2bpm where tfa = 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione, is structurally characterized and the electronic properties of the erbium metal centers is described.Structural analysis of the previously reported homodinuclear complex [Er(tfa)3]2bpm (where tfa = 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione and bpm = 2,2′-bipyrimidine) synthesized by reaction of two equivalents of ErCl3 with six equivalents of tfa and one equivalent of bpm in a basic ethanol solution is presented. X-ray quality crystals were grown by slow evaporation of concentrated methanol solution containing the complex. The complex crystallizes in the monoclinic space group P21/n, with a planar bpm ligand. The erbium…erbium distance is 6.715(5) Å. Each erbium center is eight coordinate from six tfa oxygens and two bpm nitrogens. Electronic transitions of concentrated solutions of the complex reveal three sharp lines corresponding to the 4f–4f∗ transitions at 486 nm, 520 nm and 657 nm with the lowest energy transition corresponding to 4I15/2  →  4F9/2.
Keywords: Erbium; 2,2′-bipyrimidine; Homodinuclear;

Two new pyridylalkylamide ligands containing phenol groups appended to the amide, along with their copper(II) complexes, were synthesized and characterized. A tetracopper(II) cluster, possessing a distorted cubane-like structure, a dicopper(II) species with phenoxo-bridging oxygens, and a simple monomeric copper(II) complex were synthesized and characterized.Two new pyridylalkylamide ligands containing phenol groups appended to the amide, 2-hydroxy-N-(2-pyridylmethyl)benzamide (HLPhOH) and 2-hydroxy-N-(2-pyridylethyl)benzamide (HLPhOH′), were synthesized. Copper(II) complexes of these ligands were synthesized and characterized by X-ray crystallography, ESI-MS, FTIR, UV/Vis, and EPR spectroscopy. When basic Et3N was used to deprotonate the ligands, tetracopper(II) [Cu4(LPhO)4] (1) or dicopper(II) [Cu2(LPhO′)2(CH3OH)2] (3) were formed. When base was not used, mononuclear [Cu(HLPhOH)2Cl2] (2) resulted. Complex 1 possesses a distorted cubane-like structure, with the ligands bridging via the phenoxo oxygen atoms, and the copper atoms possessing a distorted square planar geometry. The ligands in dimeric complex 3 also bridge between copper(II) atoms via the phenoxo oxygen atoms, and the copper atoms are square pyramidal. Monomeric 2 is a tetragonally distorted six-coordinate species with pyridyl N atoms and chloride ligands in the equatorial plane, and long interactions with the amide carbonyl O atoms in the axial positions.
Keywords: Copper(II) complexes; Amide ligands; N, O ligands; Multinuclear complexes;

[K(18-crown-6)(OH2)2]2[FeII(tn-OEP)(CN)2] represents the first structurally characterized Fe(II) dicyano porphyrins in a highly distorted macocyclic environment. The metal iron is on the plane of the four porphyrinic nitrogens which are accompanied by the decrease of the saddle distortion with a clear and significant increase in ruffling.Dark brown crystals of [K(18-crown-6)(H2O)2]2[FeII(tn-OEP)(CN)2] are grown by slow diffusion of cyclohexane into the THF solutions of the molecule generated via auto reduction of [FeIII(tn-OEP)Cl] in the presence of KCN and 18-crown-6 at room temperature in air and structurally characterized. The complex represents the first structurally characterized dicyano Fe(II) porphyrins in a highly distorted and sterically crowded macocyclic environment. The metal iron is on the plane of the four porphyrinic nitrogens which are accompanied by the decrease of the saddle distortion with a clear and significant increase in ruffling.
Keywords: Nonplanar porphyrins; Porphyrin core expansion; Axial coordination; Structure elucidation;

A novel branch-like one-dimensional supramolecular network structure is constructed from the self-assembly of copper(II) azamacrocyclic complex with azetidine group and iron(III) hexacyanide and it shows a weak ferromagnetic coupling between the copper(II) and iron(III) ions.The one-dimensional coordination polymer like fern branch, [CuII(L)]3[FeIII(CN)6]2·8H2O (1), which is linked by azamacrocyclic copper(II) complex and iron(III) hexacyanide, has been synthesized and characterized by single crystal X-ray crystallography and magnetic susceptibility measurement (L = 6,13-dimethyl-6-nitro-1,4,8,11-tetraazabicyclo[11.1.1]pentadecane). Compound 1 shows a weak ferromagnetic coupling between the copper(II) and low spin iron(III) ions in the one-dimensional chain structure.
Keywords: Coordination polymer; Copper(II) complex; Iron(III) hexacyanide; Crystal structure; Magnetic properties;

The heterometallic coordination polymers, {[SmMn2(imdc)2(OAc)(H2O)]·2H2O} n (1) (H3imdc = 4,5-imidazoledicarboxylic acid, HOAc = acetic acid), have been hydrothermally synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. X-ray single-crystal structural analyses reveal that 1 is three-dimensional frameworks containing Sm2Mn4 clusters. Furthermore, the luminescent properties and magnetic properties of 1 were investigated.Heterometallic coordination polymers of the form {[SmMn2(imdc)2(OAc)(H2O)]·2H2O} n (1) (H3imdc = 4,5-imidazoledicarboxylic acid, HOAc = acetic acid) were hydrothermally synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. The results reveal that 1 has a three-dimensional framework containing Sm2Mn4 clusters. The luminescence and magnetic properties of 1 were also investigated.
Keywords: Heterometallic; Coordination polymers; Luminescence; Magnetic properties;

Synthesis, structure and stability of fac-[FeII(CO)3X3]1− (X = Br, I) by Jianfeng Jiang; Wenfeng Lo; Peter Müller; Noam D. Fine; Myrium Maruani; Alexander Raytman (527-529).
fac-[FeII(CO)3X3]1− (X = Br, I) are synthesized and their structures have been determined. They are the first crystallographically characterized iron tricarbonyl trihalide complexes. fac-[FeII(CO)3X3]1− (X = Br, I) are synthesized and their structures have been determined. They are the first crystallographically characterized iron tricarbonyl trihalide complexes. fac-[FeII(CO)3X3]1− (X = Br, I) are fairly thermally stable and therefore lead themselves as excellent starting materials for the preparation of various iron carbonyl complexes since both the halide and carbonyl ligands are substitutionally labile.
Keywords: Iron carbonyl halides; X-ray structure; Infrared; Stability;

Three-dimensional fourfold interpenetrated (10, 3)-b nickel(II) framework with 5-(isonicotinamido)isophthalate by Man-Sheng Chen; Zheng-Shuai Bai; Zhi Su; Shui-Sheng Chen; Wei-Yin Sun (530-533).
A novel 3D Ni(II) coordination polymer, [Ni(INAIP)(H2O)2] n  ·  nH2O (1) [H2INAIP = 5-(isonicotinamido)isophthalic acid], has been hydrothermal synthesized and characterized. Complex 1 shows a rare fourfold interpenetrated (10, 3)-b net.A new three-dimensional nickel(II) metal-organic framework [Ni(INAIP)(H2O)2] n  ·  nH2O (1) [H2INAIP = 5-(isonicotinamido)isophthalic acid] was synthesized under hydrothermal conditions, and characterized by single-crystal X-ray structure determination, thermogravimetric analysis, X-ray powder diffraction, IR and magnetic studies. The compound 1 has (10, 3)-b topology with not well known fourfold interpenetration, in which both Ni(II) atoms and INAIP2− ligands act as three-connected nodes.
Keywords: Nickel(II) complex; Metal-organic framework; Hydrothermal reaction; (10, 3)-b Net; Fourfold interpenetration;

Synthesis, structure and magnetic properties of a copper molybdate hybrid inorganic/organic solid with a novel 10-connected three-dimensional network topology by Matthew R. Montney; Justin G. Thomas; Ronald M. Supkowski; Ryan J. Trovitch; Jon Zubieta; Robert L. LaDuca (534-539).
The mixed metal oxide phase {[Cu2(MoO4)2(4,4′-dpk)(H2O)]·H2O} n (1, 4,4′-dpk = 4,4′-dipyridylketone) exhibits [Cu2(MoO4)2(H2O)] n slabs that are pillared by 4,4′-dpk ligands into a 10-connected 3-D lattice with an unprecedented 312430526 topology. Ferromagnetic coupling within and antiferromagnetic exchange between {Cu2O2} dimers in 1 is observed.Hydrothermal reaction of CuCl2, MoO3, and 4,4′-dipyridylketone (4,4′-dpk) afforded green crystals of the mixed metal oxide phase {[Cu2(MoO4)2(4,4′-dpk)(H2O)]·H2O} n (1). According to single-crystal X-ray diffraction, {Cu2O2} dimers link into 1-D {Cu2O2(μ-H2O)} n chains via bridging aqua ligands. These chains form [Cu2(MoO4)2(H2O)] n slabs via linkage through tetrahedral molybdate anions. In turn, the copper molybdate slabs are pillared through tethering 4,4′-dpk ligands into a 10-connected three-dimensional lattice with an unprecedented 312430526 topology. Variable temperature magnetic data above 140 K were fit to the Curie–Weiss law, with C  = 0.17 cm3  K/mol Cu and Θ  = 70 K, indicating likely ferromagnetic coupling within the dinuclear kernels of 1; low temperature data points towards the possibility of interdimer antiferromagnetic interactions.
Keywords: Copper; Molybdate; Diimine; Coordination polymer; Ferromagnetism;

Mercury(II) cyanide reacts with 1,4-diaminobutane (bn) at a 1:1 ratio forming a polymeric complex [(bn)Hg(CN)2] in which (bn) acts as a bridge between the Lewis acid Hg(CN)2 moieties.Mercury(II) cyanide reacts with 1,4-diaminobutane (bn) at a 1:1 ratio forming a polymeric complex [(bn)Hg(CN)2] in which (bn) acts as a bridge between the Lewis acid Hg(CN)2 moieties. The metal complex coordination sphere Hg[(CN)2N2] is best described as distorted trigonal pyramidal. The 13C and 15N CP MAS NMR data show two chemically different CN groups consistent with the hydrogen bonding scheme involving only one of the cyano ligands.
Keywords: 1,4-Diaminobutane; Mercury(II) cyanide; X-ray structure; 199Hg, 13C and 15N CP MAS NMR;

Characterization of the first hexacoordinate phosphorus compound with S→P←S bonds by K.V.P. Pavan Kumar; M. Phani Pavan; K.C. Kumara Swamy (544-547).
Synthesis and X-ray structure of the first example of a hexacoordinate phosphorus compound [S{6-t-Bu-4-Me-C6H2O}2]2P+[Cl·(C3H4N2)] with two S→P bonds is reported. This novel compound can be construed as an oxophosphonium salt with double intramolecular coordination by sulfur atoms.The first example of a hexacoordinate phosphorus compound [S{6-t-Bu-4-Me-C6H2O}2]2P+(Cl·C3H4N2) with two S→P bonds is reported. This compound can be construed as an oxophosphonium salt with double intramolecular coordination by sulfur atoms. X-ray structure reveals a facial arrangement of the ligands with two coordinating sulfur atoms cis to each other. The S→P distance of 2.334 (1) Å is one among very short coordinate bond distances between sulfur and phosphorus.
Keywords: Hypervalency; Phosphorane; Phosphonium salt; Coordination geometry; Structure;

Two 3D coordination polymers with the flexible tripodal ligand ttmb (1,3,5-tris(1,2,4-triazol-1-ylmethyl)benzene), [M2(ttmb)2(SO4)2(H2O)2] · 7H2O (M = Cd or Mn), have been synthesized and structurally characterized. They are isostructural and possess a 3D architecture fused from 2D (4,4) M(ttmb) networks and MSO4 chains by sharing “hinge” metal atoms. The thermal, luminescent and magnetic properties have been studied.Two 3D organic–inorganic hybrid coordination polymers, [M2(ttmb)2(SO4)2(H2O)2] · 7H2O (M = Cd, 1; M = Mn, 2; ttmb = 1,3,5-tris(1,2,4-triazol-1-ylmethyl)benzene), have been synthesized and structurally characterized. They are isostructural and possess a 3D architecture fused from 2D (4,4) M(ttmb) networks and MSO4 chains by sharing “hinge” metal atoms. The thermal properties of 1 and 2, luminescent property of 1 as well as magnetic property of 2 have been investigated.
Keywords: Coordination polymers; Flexible ligands; Crystal structures; Tripodal ligands; 1,2,4-Triazol;

A novel Co(II) phosphonate [Co(aepa)(4,4′-bpy)(H2O)2]·2H2O 1, has been synthesized by hydrothermal reaction using 2-aminoethylphosphonic acid (H2aepa). Compound 1 features a 3D honeycomb network structure originating from the intertwist of the rare sixfold 1D helical chains, which are assembled from the coordination of the aepa2− ligands to the cobalt atoms.A new cobalt(II) phosphonate, [Co(aepa)(4,4′-bpy)(H2O)2]·2H2O 1 (H2aepa = 2-aminoethylphosphonic acid) has been hydrothermally synthesized and characterized by IR, elemental analysis, TGA and single crystal X-ray diffraction analysis. Compound 1 features a 3D alveolate network structure originating from the intertwist of the rare sixfold 1D helical chains, which are assembled from the coordination of the aepa2− ligands to the cobalt atoms.
Keywords: Helix; Sixfold screw axis; Crystal structure; Phosphonate;

A Michael-type addition occurs between one amino group from ethylenediamine and two acrylato ions coordinated to nickel(II), resulting in the dianion of the ethylenediamine-N,N-dipropionic acid. The final product is a carboxylato-bridged binuclear nickel(II) complex.The reaction between NiCO3  · Ni(OH)2, acrylic acid and ethylenediamine in a 2:4:1 molar ratio affords the binuclear complex, [Ni2(EDDP)2(H2O)2] · 2H2O 1. The organic ligand, EDDP2− (the dianion of the ethylenediamine-N,N-dipropionic acid ligand), results from the addition of one amine group to the carbon–carbon double bonds of two acrylato ions. The crystal structure of 1 consists of neutral centrosymmetric entities, with the nickel ions connected by two carboxylato groups, each one acting as a monoatomic bridge. The intramolecular Ni⋯Ni distance is 3.212 Å. The metal ions exhibit an octahedral geometry. The cryomagnetic investigation of 1 reveals an antiferromagnetic coupling of the nickel(II) ions (J  = −21.8 cm−1, H  = −J S Ni1 S Ni2).
Keywords: Nickel complexes; Carboxylato-bridged complexes; Crystal structure; Magnetic properties;

Two supramolecular nickel-organic frameworks, [Ni(HBTC)(bix)] n (1) and [Ni3(BTC)2(mbix)3(H2O)4] n  · 6nH2O (2) (bix = 1,4-bis(imidazole-l-yl-methyl)benzene, mbix = 1,3-bis(imidazole-l-yl-methyl)benzene, and H3BTC = 1,3,5-benzenetricarboxylate), were obtained under hydrothermal reactions. The 3D supramolecular structure of compound 1 exhibits a rarely encountered 3D (4, 6)-connected fsc topological net when hydrogen-bonging interactions between the adjacent layers are taken into account. Compound 2 manifests an unprecedented 2D (3, 4)-connected topological net. Close ππ stacking interactions occur between the adjacent layers of compound 2. The magnetic studies show that compound 1 features overall ferromagnetic property. Whereas compound 2 was treated as a mononuclear model, which presents strong zero-field splitting (ZFS). Furthermore, the IR and TGA properties of 1 and 2 were also studied.Two supramolecular nickel-organic frameworks, [Ni(HBTC)(bix)] n (1) and [Ni3(BTC)2(mbix)3(H2O)4] n  · 6nH2O (2) (bix = 1,4-bis(imidazole-l-yl-methyl)benzene, mbix = 1,3-bis(imidazole-l-yl-methyl)benzene, and H3BTC = 1,3,5-benzenetricarboxylate), have been hydrothermally prepared by the assembly of H3BTC, Ni2+ with bix or mbix. Compound 1 shows a 2D layer structure, whose 3D supramolecular structure exhibits a fsc topology when hydrogen-bonging interactions between the adjacent layers are taken into account. Compound 2 manifests an unprecedented 2D (3, 4)-connected topological net. The 3D supramolecular framework of 2 is formed through ππ stacking interactions between the adjacent layers. The magnetic studies show that 1 features overall ferromagnetic property whilst 2 presents strong zero-field splitting (ZFS) when treated as a mononuclear model. Furthermore, the IR and TGA properties of 1 and 2 were also studied.
Keywords: Metal-organic frameworks; Crystal structures; Topological analyses; Magnetic properties;

Two 1D coordination polymeric isomers with the same chemical formula [Cu(2,2′-bipy)(Htda)] n : Synthesis, crystal structures and electrochemical properties by Guang-Fei Liu; Ling-Ling Li; Yu-Shu Ren; Hong-Xi Li; Zhi-Gang Ren; Yong Zhang; Jian-Ping Lang (563-565).
Two 1D coordination polymeric isomers with the same chemical formula [Cu(2,2′-bipy)(Htda)] n (2,2′-bipy = 2,2′-bipyridine, Htda = 1,2,3-triazole-4,5-dicarboxylate) were isolated from solvothermal reactions of [Cu(MeCN)4](ClO4)2 with 2,2′-bipy and H3tda. Both complexes were structurally characterized by elemental analysis, IR, and X-ray crystallography and their electrochemical properties were studied.Two 1D coordination polymeric isomers with the same chemical formula [Cu(2,2′-bipy)(Htda)] n (2,2′-bipy = 2,2′-bipyridine, Htda = 1,2,3-triazole-4,5-dicarboxylate) were solvothermally prepared and structurally characterized. X-ray analysis revealed that one isomer has a 1D staircase chain structure while the other possesses a 1D spiral chain structure. The electrochemical behaviors of both isomers in solution were also investigated by cyclic voltammetry.
Keywords: Coordination polymeric isomers; Solvothermal synthesis; Crystal structure; 1H-1,2,3-Triazole-4,5-dicarboxylic acid; Electrochemical properties;

A novel 12-tungstovanadate and 3d–4d heterometallic complex hybrid compound [V1W12O40][VO2Ag(phen)3]2 by Ming-xing Yang; Shen Lin; Li-juan Chen; Xiao-feng Zhang; Hui-hong Xu (566-568).
An uncommon bisupporting polyoxometalate derivative in which the saturated Keggin type polyoxoanions are covalently linked by bimetallic complex [VO2Ag(phen)3]2+. The compound shows good photocatalytic activity for reduction of Rhodamine B (RB) in a liquid–solid system.A novel organic–inorganic hybrid compounds containing 12-tungstovanadate and 3d–4d heterometallic complex, [V1W12O40][VO2Ag(phen)3]2 (1), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction and IR analysis. The complex is an uncommon bisupporting polyoxometalate derivative in which the saturated Keggin type polyoxoanions are covalently linked by bimetallic complex [VO2Ag(phen)3]2+. The neighboring Ag+ and V5+ cations are bridged by the oxo atom forming heterometallic cations with the Ag–V distances of 3.556(2) Å in [VO2Ag(phen)3]2+ cations. Furthermore, the title compound shows good photocatalytic activity for reduction of Rhodamine B (RB) in a liquid–solid system.
Keywords: Polyoxotungstates; Hydrothermal synthesis; Photocatalysis;

Catalytic alcoholysis of quinolin-8-yl esters by manganese complexes by Dipjyoti Kalita; Rupam Sarma; Jubaraj B. Baruah (569-571).
Methanolysis of p-nitrobenzoic acid quinolin-8-yl ester is catalysed by manganese(II) acetate tetrahydrate under aeorobic condition. This catalytic reaction involves Mn(II) as well as Mn(III) ions.The role of different oxidation states of manganese in manganese(II) acetate promoted methanolysis reaction of p-nitrobenzoic acid quinolin-8-yl ester is presented.
Keywords: Quinolin-8-yl esters; Alcoholysis; Catalysis; Manganese complexes; Crystal structures;

Synthesis, structures and catalytic properties of palladacycles derived from N,N-dimethylaminomethylferrocene by Xiao-Sheng Yang; De-Liang Long; Hua-min Li; Zhong-Lin Lu (572-575).
Palladacycles 24 containing the N,N-dimethylaminomethylferrocenyl backbone and three pyridine co-ligands have been prepared and structurally characterized. Their catalytic activities in promoting the methanolysis of the pesticide parathion were investigated.Cyclopalladated complexes with a N,N-dimethylaminomethylferrocenyl (dmaf) backbone and three pyridine co-ligands, [Pd{(η5-C5H5)Fe[(η5-C5H3)CH2NMe2]}Cl(R-Py)] (2: R = 4-H; 3: R = 4-cyano; 4: 4-N,N-dimethylamino) have been synthesized and characterized. The single crystal X-ray diffraction analyses show that the palladium(II) in both 3 or 4 is coordinated in a distorted square planar geometry with the two nitrogen atoms trans to each other. The three palladacyles were shown to greatly catalyze the methanolysis of the P=S containing pesticide parathion but showed different accelerations. It was found that the replacement of phenyl by ferrocenyl in the palladacycle backbone of 2 lowers the kinetic pKa s s of the Pd-(HOCH3) required for activity by almost 2 units.
Keywords: Palladacycle; Ferrocene; Methanolysis; Pesticides; Crystal structure;

The reaction of platinum(II) complex [PtMe2(bu2bpy)] (bu2bpy = 4,4′-di-tert-butyl-2,2′-bipyridine) with 1,2-dibromotetrachloroethane gives unexpected products of trans-[PtMe2BrCl(bu2bpy)] and [PtCl2(bu2bpy)]. The crystal structure of trans-[PtMe2BrCl(bu2bpy)] shows that platinum adopts an octahedral geometry.The platinum(II) complex [PtMe2(bu2bpy)] (bu2bpy = 4,4′-di-tert-butyl-2,2′-bipyridine) (1) reacted with 1,2-dibromotetrachloroethane in a 2:1 mole ratio of Pt(II): (CBrCl2)2 to afford trans-[PtMe2BrCl(bu2bpy)] (2) and [PtCl2(bu2bpy)] (3). The 1H NMR spectroscopy shows that the Pt–Me bond cleavage is mainly involved after a fast oxidative addition reaction. Complex trans-[PtMe2BrCl(bu2bpy)] (2) has been characterized by X-ray diffraction which shows that platinum adopts an octahedral geometry.
Keywords: Platinum; Oxidative addition; Spectroscopy; Crystal structure; Geometry;

Synthesis, structure and properties of the mixed-ligand tungsten(II) complex [WBr2(CO)3(tmpymt)] (tmpymt = 1,4,6-trimethylpyrimidine-2-thione) by Viviane A.S. Falcomer; Sebastião S. Lemos; José R.S. Politi; Gleison A. Casagrande; Ernesto S. Lang; Robert A. Burrow (580-582).
In the mononuclear seven-coordinated complex [WBr2(CO)3(tmpymt)]·C3H6O the WII atom adopts a distorted capped trigonal prism (CTP) geometry. The single-crystal X-ray molecular structure was compared to the optimized molecular structure (RHF/LanL2DZ) and the results are convergent to CTP geometry.The reaction of [{WBr(CO)4}2(μ-Br)2]2 1 with 1,4,6-trimethylpyrimidine-2-thione (tmpymt) affords the air-sensitive complex [WBr2(CO)3(tmpymt)] 2. The X-ray structure of 2·C3H6O reveals that the geometry surrounding the tungsten(II) atom is best described as a distorted capped trigonal prism with a bromine atom Br(1) in the unique capping position. The other bromine atom Br(2), the (N,S)-chelate and one carbonyl C(41) occupy the capped quadrilateral face. The complex has been additionally characterized by IR and NMR spectroscopy. The optimized molecular structure (RHF/LanL2DZ) supports the experimental data.
Keywords: Pyrimidinethione; Halocarbonyl complexes; Seven-coordinated tungsten(II) complexes; X-ray crystallography;

Phenanthroline citrate zinc complexes [Zn(Hcit)(phen)(H2O)][Zn2(Hcit)(phen)2(H2O)3]·13.5H2O (1) and its aggregate [Zn3(Hcit)2(phen)4] n ·14nH2O (2) are isolated in weak acidic solution. The formations of the two complexes are sensitive to the molar ratio of the reactants. Transformations of the two complexes are reversible in 72% and 77% yield, respectively, showing an equilibrium between 1 and 2.Adduct of mononuclear and dinuclear citrate zinc complex [Zn(Hcit)(phen)(H2O)][Zn2(Hcit)(phen)2(H2O)3]·13.5H2O (1) and its aggregate [Zn3(Hcit)2(phen)4] n ·14nH2O (2) (H4cit = citric acid, phen = 1,10-phenanthroline) were synthesized in weak acidic solutions. The former was obtained from the reaction of zinc nitrate, citric acid and phenanthroline in a molar ratio of 3:2:3, while a slightly excess of phenanthroline results in the formation of the polymeric product 2 in a molar ratio of 3:2:4. Transformation of 1 to 2 was finished by the reaction of 1 with an equimolar of phenanthroline in 72% yield. Reverse conversion of 2 to 1 is obtained in 77% yield, showing an equilibrium between 1 and 2. Neutral compound 1 consists of one monomeric anionic unit [Zn(Hcit)(phen)(H2O)] and one dimeric cationic unit [Zn2(Hcit)(phen)2(H2O)3]+ that connect each other by strong hydrogen bonds [O6⋯O4w 2.636(2); O7⋯O3w 2.630(3) Å]. In 2, the citrate ligand links each trinuclear unit [Zn3(Hcit)2(phen)4] to generate an infinite 1D chain that extents into a 3D supramolecular structure by intra- and inter-molecular hydrogen bonds. Moreover, 1 and 2 exhibit strong fluorescence at room temperature.
Keywords: Zinc; Citric acid; Crystal structure; Mixed ligands; Interconversion;

The direct mixing of Ru ( bpy ) 3 2 + and yeast alcohol dehydrogenase leads to luminescent, Ru ( bpy ) 3 2 + -containing supramolecular materials which can form very stable film exhibiting excellent electrochemiluminescene behaviors on bare electrode surfaces.In this communication I report on a solution-based assembly strategy for the preparation of Ru ( bpy ) 3 2 + -containing luminescent materials with the use of yeast alcohol dehydrogenase (YADH) as a supramolecular assembly agent, involving the direct mix of concentrated Ru(bpy)3Cl2 and YADH aqueous solutions at room temperature. It is unexpectedly found that the resulting assemblies can form very stable film on bare electrode surfaces and at the same time exhibit excellent electrochemiluminescene (ECL) behaviors and therefore, provide us a novel kind of easily-immobilized luminescent materials for solid-state ECL detection in capillary electrophoresis (CE) or CE microchip.
Keywords: Nanostructures; Electron microscopy; Yeast alcohol dehydrogenase; Luminescence;