Inorganic Chemistry Communications (v.62, #C)

Contents List (iii-x).

In-situ hydrothermal preparation of a novel 3D CuI-based tetrazole coordination polymer with pseudo-porphyrin secondary building units by Dapeng Dong; Naisen Yu; Yan Cong; Ying Zhao; Haiyan Zhao; Dedi Liu; Zhenghua Li; Jia Liu; Dongping Liu (1-4).
A novel 3D CuI-based tetrazole coordination polymer through the employment of in-situ hydrothermal techniques by using 4-cyanopyridine, NaN3 and CuI, [Cu5(L)3I2] (1) (HL = 5-(4-Pyridyl)-1H-tetrazole) has been synthesized and structurally characterized by X-ray single-crystal diffraction as well as by powder X-ray diffraction, elemental analysis and thermogravimetric analysis. In compound 1, each CuN3I tetrahedron, CuN2I2 tetrahedron and CuN3 triangle are linked to each other by L ligand to form a 3D framework structure. It is interesting to note that the interconnection of Cu1 and Cu2 ions by bridging L ligand form pseudo-porphyrin secondary building units. Surface photovoltage, field-induced surface photovoltage and luminescent properties of compound 1 have also been studied.A novel 3D CuI-based tetrazole coordination polymer through the employment of in-situ hydrothermal techniques by using 4-cyanopyridine, NaN3 and CuI has been synthesized. The compound has pseudo-porphyrin secondary building units. Surface photovoltage, field-induced surface photovoltage and luminescent properties of the compound have also been studied.Display Omitted
Keywords: Crystal structure; Surface photovoltage; Luminescence; Copper(I) iodide;

Complexes of the type [RhII 2(CO3)4(H2O)L]n − with L = N-methylpyrazinium+ and 1-heptyl-4-(4-pyridinyl)pyridinium+ cations display intense long-wavelength (Rh(II) to L) MLCT absorptions. With L = H2O, MLCT absorptions are not identified, but the photoreactivity of the complex in aqueous solution supports the assumption that (Rh(II) to CO3 2 −) MLCT excited states are accessible. Upon irradiation with white light, Rh(II) is photooxidized while carbonate is reduced to CO. The efficiency of this photolysis is very low. However, the occurrence of this photoredox reaction is, nevertheless, of general interest with regard to the photochemical reduction of CO2.The Rh(II)2 bond serves as CT-donor in the complexes [Rh2(CO3)4]xLn with L = H2O and N-methylpyrazinium+/N-heptyl-4,4´-bipyridyl. With L = H2O the photolysis leads to the oxidation of Rh(II) and reduction of carbonate to CO.Display Omitted
Keywords: Photochemistry; Rhodium(II); Carbonate; Photoreduction of CO2; MLCT excitation;

A rhenium(I) compound bearing a dimerized chromone NO bidentate chelator by Irvin Noel Booysen; Ifeoma Ebonumoliseh; Matthew Piers Akerman; Bheki Xulu (8-10).
Herein, we communicate the synthesis of a novel rhenium(I) complex, fac-[Re(CO)3(chrpychr)Br] (1) from the equimolar reaction between 2-(4-oxo-4H-chromen-3-yl)-5H-chromeno[2,3-d]pyrimidin-5-one (chrpychr) and [Re(CO)5Br]. The metal complex 1 was characterized via 1H NMR-, IR- and UV–Vis spectroscopy and conductivity measurements. Single crystal X-ray analysis provides definitive confirmation in the structural elucidation of 1. DFT studies of 1 aided in the interpretation of its experimental IR spectrum.A novel rhenium(I) complex, fac-[Re(CO)3(chrpychr)Br] was isolated from the equimolar reaction between 2-(4-oxo-4H-chromen-3-yl)-5H-chromeno[2,3-d]pyrimidin-5-one (chrpychr) and [Re(CO)5Br].Display Omitted
Keywords: Rhenium; Chromone; Spectral characterization; DFT studies; Crystal structure;

A facile synthesis of water-soluble BaYF5:Ln3 + NCs with excellent luminescent properties as promising contrast agent for dual-modal bioimaging by Cailing Chen; Chunguang Li; Liang Zhao; Xiaomin Liu; Tianyu Bai; He Huang; Zhan Shi; Shouhua Feng (11-14).
Monodisperse, water-dispersible lanthanide (Ln3 +)-doped BaYF5 nanocrystals (NCs) are synthesized through a fast, facile and environmentally–friendly microwave-assisted modified polyol process with polyethyleneimine as the surfactant. The TEM images illustrate the sphere-like and flower-like morphologies of the obtained NCs. Intense multicolor down conversion (DC) luminescence is also achieved in Ce3 +/Ln3 + (Ln = Tb, Dy) doped BaYF5 NCs. Then, upon excitation at 980 nm, upconversion (UC) luminescent properties of BaYF5:Yb3 +/Ln3 + (Ln = Er, Tm, Ho) NCs and energy transfer between Yb3 + and Ln3 + are systematically surveyed. Furthermore, a layer of SiO2 is coated on the surface of the NCs and the methyl thiazolyl tetrazolium (MTT) assays are performed to test the cytotoxicity of BaYF5:Ln3 + NCs. Due to the X-ray absorption property of Ba element, a proof-of-concept CT imaging with BaYF5:Ln3 + NCs is conducted. These results indicate that the obtained NCs have great potential as optical/CT bioprobe.Monodisperse, water-dispersible BaYF5:Ln3 + nanospheres and nanoflowers were synthesized via microwave-assisted modified polyol process. The obtained NCs with excellent up-down luminescent property and X-ray absorption property have great potential as optical/CT bioprobe.Display Omitted
Keywords: Nanocrystals; Up-down conversion; Lanthanide; Bioimaging agent;

Host-guest structural architectures in hydrous alkaline (Li, K) uranyl chromates and dichromates by Evgeny V. Nazarchuk; Oleg I. Siidra; Anastasiya I. Zadoya; Atali A. Agakhanov (15-18).
Two new (Cr2O7)2 − and/or (CrO4)2 − containing uranyl compounds with K and Li: [K10(Cr2O7)2(H2O)2]|(UO2)(CrO4)4  | (1) and | Li2(H2O)5  |[(UO2)(CrO4)2] (2) were obtained via two various synthesis routes in the K2Cr2O7–CrO3–(UO2)(NO3)2·6H2O–H2O (1) and LiCl–CrO3–(UO2)(NO3)2·6H2O (2) systems. The key feature of the crystal structure of 1 is the formation of hydrous potassium dichromate [K10(Cr2O7)2(H2O)2]6 + 2D units acting as hosts for guest |(UO2)(CrO4)4  |6 − clusters. (Cr2O7)2 − groups are not bonded via common oxygen atoms to (UO2)2 + in 1 which is the first example of such structural architecture in uranyl oxysalts with tetrahedral TO4 (T  = Si4 +, As5 +, P5 +, Cr6 +, etc.) anions. In the structure of 2, UrO5 and CrO4 coordination polyhedra share corners to produce [(UO2)(CrO4)2]2 − layers with | Li2(H2O)5  |2 + tetramers guest species in the interlayer.Two new uranyl chromate-dichromate compounds with K and Li with two different host-guest structural architectures.Display Omitted
Keywords: Uranium; Chromium; Potassium dichromate; Coordination modes; Host–guest structures;

A “naked eye” and ratiometric chemosensor for cobalt(II) based on coumarin platform in aqueous solution by Zhaodi Liu; Wenlong Wang; Huajie Xu; Liangquan Sheng; Shuisheng Chen; Deqian Huang; Fei Sun (19-23).
A novel ratiometric and colorimetric cobalt(II) chemosensor (HL) based on coumarin platform has been synthesized. It displayed a remarkable (44 nm) red-shift in the absorption spectra upon reaction with Co2 +, which is easily observed from yellow to red by the naked-eye. Co2 + could be quantitatively detected in the range of 0–10 μM by both normal and ratiometric absorption spectrometry methods. The detection limit of HL for Co2 + detection was as low as 0.31 μM.A ‘‘naked eye’’ and ratiometric chemosensor HL for Co2 + ion based on coumarin platform has been synthesized and fully characterized. The binding structure between HL and Co2 + was given by Job’s plot, IR spectrometry, MALDI-TOF mass spectra.Display Omitted
Keywords: Cobalt(II); Colorimetric; Ratiometric chemosensor; Coumarin;

Organic–inorganic hybrid supramolecular assembly through the highest connectivity of a Wells–Dawson molybdoarsenate by Honghong Cai; Jinghua Lü; Kai Yu; He Zhang; Chunmei Wang; Lu Wang; Baibin Zhou (24-28).
An unusual supramolecular hybrid material based on the Dawson molybdoarsenate, (H2bimyb)3(As2Mo18O62) (1) (bimyb = 1,4-Bis(imidazol-l-ylmethyl) benze) has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, UV, XRD, and single-crystal X-ray diffraction. In compound 1, the {As2Mo18O62} cluster uses its surface oxygen atoms to attract 14 bimyb ligands, which are further surrounded by 22 Dawson polyanions via strong supramolecular interactions to form close-packed 3D supramolecular networks with a (1491)(510)(46) topology structure. Compound 1 represents the highest connectivity of Dawson molybdoarsenate. In addition, compound 1 exhibits bifunctional electrocatalytic behaviors for oxidation of ascorbic acid (AA) and reduction of hydrogen peroxide (H2O2), as well as high-efficient degradation ability for typical dye MB under UV light.Organic ligand bimyb is firstly introduced into the {As2Mo18} hybrid system to yield a close-packed 3D supramolecular network. Compound 1 represents the highest connectivity of Dawson molybdoarsenate, which exhibits bifunctional electrocatalytic behavior for oxidation of AA and reduction of H2O2, as well as high-efficient degradation ability for MB under UV light.Display Omitted
Keywords: Supramolecular; As2Mo18O62 6 −;  Electrocatalysis; Photocatalysis;

{[Cu4(μ-bpe)4Cu2(μ-pydc)23-pydc)2]·14H2O}n (1) and [Cu(pydcH)2(bpe)2] (2) have been solvothermally synthesized by 1,2-bis(4-pyridyl)ethylene (bpe) along with dianionic pyridine-2,3-dicarboxylate (pydc) ligands and characterized by elemental, FT-IR and thermal analyses techniques. In the solvothermal synthesis of complexes, 1 was isolated when the reactor was opened whereas 2 was crystallized after 3 weeks. The X-ray crystallographic studies show that complex 1 exhibits ladder-like structure involving mixed-valence Cu(I,II) which has generated a simultaneous in situ redox reaction and a unique 14-membered water cluster consisting of an eight-membered open-cube hexamer and two cyclic water trimers has been observed in hydrophilic cavities of 1. Supramolecular network of 2, which has proton transfer product of pydcH cations, is formed by O–H···N and aromatic interactions.Two new copper organic networks are solvothermally synthesized in one pot. In 1, 1D ladder-like structure consists of mixed valence Cu(I, II), which is obtained by an in situ redox reaction and it has a unique 14-membered water cluster. Complex 2 has proton transfer product and it is formed by O–H···N and aromatic interactions.Display Omitted
Keywords: Coordination polymers; Pyridine-2,3-dicarboxylate; 1,2-bis(4-pyridyl)ethylene; Solvothermal synthesis; Water clusters; Mixed-valence Cu(I, II); One-pot synthesis;

A hybrid polyoxometalate-aminoazobenzene dye compound, (C12H12N3)3PW12O40 2CH3CN (1) has been synthesized in CH3CN/H2O solution under conventional reaction conditions. The structure of 1 was determined by single-crystal X-ray diffraction, and further characterized by IR spectroscopy, UV–vis spectra and diffuse reflectance spectra. The absorption edge of 1 is largely red-shifted compared to the pure polyoxoanions, due to the introduction of the dye cations. Photocatalytic studies indicated that compound 1 exhibits effective photocatalytic H2 evolution activity under visible-light.A hybrid polyoxometalate-aminoaobenzene dye compound has been synthesized under conventional reaction conditions, and photocatalytic studies indicated that the title compound exhibits effective photocatalytic H2 evolution activity under visible-light.Display Omitted
Keywords: Polyoxometalates; Organic dye cations; Visible light; Photocatalytic H2 evolution;

Characterization of molecular mechanism of neuroglobin binding to cytochrome c: A surface plasmon resonance and isothermal titration calorimetry study by Purushottam Babu Tiwari; Luisana Astudillo; Khoa Pham; Xuewen Wang; Jin He; Sophie Bernad; Valérie Derrien; Pierre Sebban; Jaroslava Miksovska; Yesim Darici (37-41).
Neuroglobin (Ngb) is a six-coordinate heme protein predominantly expressed in the brain tissue with a protective role against hypoxic/ischemic and oxidative stress-related insults. Several intracellular proteins including cytochrome c have been identified as potential neuroglobin binding partners. To understand the factors that control Ngb association to cytochrome c (Cyt c) the thermodynamic parameters for Cyt c association to Ngb variants were probed using surface plasmon resonance and isothermal titration calorimetry techniques. The dissociation constant for human Ngb binding to Cyt c was determined to be ~ 10 μM using SPR and a similar value was obtained by ITC confirming that the covalent attachment of Cyt c to the gold surface modified with mixed alkanethiols does not impair Cyt c interactions with Ngb. Modification of the heme iron coordination sphere by replacement of histidine 64 in the position of sixth axial ligand with cyanide effectively inhibits the inter-protein complex formation. On the other hand, the presence of the Cys 46/Cys 55 disulfide bridge that restrains the CD loop flexibility and increases the distal histidine affinity for heme iron has no impact on complex stability. ITC data also show that the inter-protein complex formation is entropy driven (ΔH = 3.3 ± 0.2 kcal mol− 1 and ΔS = 32.3 cal mol− 1  K− 1) likely due to a reorganization of solvent molecules surrounding charged amino-acid residues. The experimental data are consistent with the results of a docking study in which the residues in the E- and F-helix of Ngb were identified to form a binding site for Cyt c. We propose that association of the exogenous ligand to the heme iron triggers a repositioning of the E-helix that prevents Ngb-Cyt c complex formation.
Keywords: CD loop; SPR sensor; Electrochemical impedance spectroscopy; E-helix; Disulfide bridge;

An ether bridged tetracarboxylic acid ligand, 5-(3′,4′-Dicarboxylphenoxy)-isophthalic acid (H4L) was used to construct two Co(II) coordination polymers in presence of different nitrogen donor ligands such as 4,4′-bipyridine (4,4′-bpy) and 4,4′-bis(pyrid-4-yl)biphenyl (bpbp). The products formed under hydrothermal conditions are formulated as [Co2L(4,4′-bpy)2(H2O)3]n (1) and {[Co(bpbp)2(H2L)]·H2O}n (2). The compounds were characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis, and powder X-ray diffraction (PXRD) measurement. Compound 1 shows an intriguing (3,4,5)-connected 3D framework with a point symbol of (42  · 62  · 82)(42  · 65  · 83)(62  · 8). Compound 2 is an unusual 3D supramolecular framework generated by the one-dimensional [Co(bpbp)(H2L)]n polymer chain. The magnetic properties of compounds 1 and 2 were examined, indicating antiferromagnetic interactions between the cobalt(II) ions in the temperature range of 2–300 K.Two new coordination polymers with ether bridged tetracarboxylic acid ligand 5-(3′,4′-Dicarboxylphenoxy)-isophthalic acid (H4L) and different nitrogen donor ligands, including 4,4′-bipyridine (4,4′-bpy) and 4,4′-bis(pyrid-4-yl)biphenyl (bpbp) have been hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction analyses indicate that compound 1 is a 3D framework, whereas compound 2 shows a 3D supramolecular framework with 1D chain. The magnetic properties of complexes 1 and 2 were examined, indicating antiferromagnetic interactions between the cobalt(II) ions in the temperature range of 2–300 K.Under solvothermal condition, the reaction of Co(II) acetate with mixed-ligands 5-(3′,4′-Dicarboxylphenoxy)-isophthalic acid (H4L), 4,4′-bipyridine (4,4′-bpy) and 4,4′-bis(pyrid-4-yl)biphenyl (bpbp) affords two new coordination polymers.Display Omitted
Keywords: Coordination polymers; Antiferromagnetic interactions; Crystal structure;

A new 3D pillared-layer porous framework with intersecting open channels in the Co/triazolate/carboxylate system: Synthesis, structure and magnetism by Shao-Bin Miao; Bao-Ming Ji; Yu-Fang Wang; Zhao-Hao Li; Dong-Sheng Deng; Chun-Ying Xu; Le Zhou (47-50).
A new Co(II) coordination polymer, namely [Co6(btc)4(dtb)2(H2O)3]n (1) (H3btc = 1,3,5-benzenetricarboxylic acid, dtb = 1,3-di-(1,2,4-triazole-4-yl)benzene), has been synthesized by combining the mixed ligands of H3btc and dtb with Co(Ac)2·4H2O under solvothermal conditions. Single-crystal X-ray diffraction analysis reveals that 1 feature a 3D open framework with intersecting channels based on Co-btc3 − layers and btc3 − and dtb pillars. The magnetic property of the complex has also been investigated at room temperature.A new Co(II) coordination polymer, namely [Co6(btc)4(dtb)2(H2O)3]n (1) (H3btc = 1,3,5-benzenetricarboxylic acid, dtb = 1,3-di-(1,2,4-triazole-4-yl)benzene), has been synthesized. Compound 1 features a 3-D open framework with intersecting channels based on Co-btc3 − layers and btc3 − and dtb pillars.Display Omitted
Keywords: 1,3-Di-(1,2,4-triazole-4-yl)benzene; Coordination polymers; Crystal structure; Magnetism;

Ag(I)-triazolylcarboxylates: The role of hydrocarbon tails in the formation of “sitting-on-layer” supramolecular bowls by Sergiy I. Vasylevs'kyy; Andrey B. Lysenko; Harald Krautscheid; Miroslaw Karbowiak; Eduard B. Rusanov; Konstantin V. Domasevitch (51-54).
Several α-amino acids, (l,d)-alanine and (l,d)-phenylalanine were utilized, as precursors for synthesis of 1,2,4-triazolyl carboxylic acids (l,d)- trala-H and (l,d)- trphe-H, which were explored as angular bifunctional building blocks for engineering Ag(I)-coordination polymers. Two complexes, [Ag(μ 4-trala)]·H2O (1) and [Ag(μ 4-trphe)]·H2O (2), were prepared under mild hydrothermal conditions and characterized. The organic ligands coordinate silver cations in a deprotonated form via a N2O2 donor set, where the tr group behaves in a [N–N] mode while the carboxylate function serves as a μ220 bridge. Complexes 1 and 2 possess a layered structure consisting of [Ag([N–N]-tr)(COO)]n chains which are interlinked through ligand spacers. Being oriented toward the neighboring layers, the hydrocarbon side “tails” display a peculiar role in the supramolecular organization of “sitting-on-layer” three-dimensional baskets. Each container is pleasantly suitable for binding a water molecule via an H-bonding acceptor portal of carboxylate fragments.1,2,4-Triazolyl carboxylic acids, the angular molecular tectons derived from natural alpha-amino acids, were employed for engineering Ag(I)-coordination polymers. The presence of hydrocarbon side tails in ligand structures resulted in unique “sitting-on-layer” supramolecular bowls which are perfectly fitted to encapsulate water molecules.Display Omitted
Keywords: Ag(I) coordination polymers; 1,2,4-triazolyl carboxylic acids; Supramolecular containers; Host-guest interactions; Photoluminescence properties;

Pro-oxidant activity of nickel (II) pyridoxal complexes. Synthesis, characterization and peroxidase activity assays by Liniquer Andre Fontana; Mônica Stüker; Gelson Manzoni Oliveira; Bernardo Almeida Iglesias; Davi Fernando Back (55-59).
The synthesis of Ni (II) complexes with pro-oxidant applications has demonstrated many advantages, such as accelerated reactions, solution stability and with high selectivity reactions. In this work we describe the synthesis, characterization and structural analysis of nickel ([(Ni)(C30H28N4O4S2)]);([(Ni)(C31H30N4O4S2)]) and ([(Ni)(C33H37N4O4S2)]·DMF — complex 3) complexes with ligands obtained from the condensation of pyridoxal and aryl-thiol amines and their application as a pro-oxidant in the reaction of the phenol-aminoantipyrine adduct. The complexes show variation in carbon spacers between pyridoxal molecules: ethane, propane and butane. It was found that the spacer two carbons containing the most significant as the pro-oxidant activity.Ni(II)-pyridoxal complexes with preliminar peroxidase activity.Display Omitted
Keywords: Pyridoxal; Nickel complexes; Peroxidase mimetization;

Synthesis, structure and magnetic properties of a tetranuclear Mn(II) complex with carbohydrazone based ligand by Rahman Bikas; Hassan Hosseini-Monfared; Milosz Siczek; Serhiy Demeshko; Behzad Soltani; Tadeusz Lis (60-63).
A new tetranuclear complex of Mn(II), [Mn4(L)2(CH3OH)2(μ-N3)4(N3)2] ∙ 2(CH3OH) (1), was synthesized and characterized by spectroscopic methods, single-crystal X-ray diffraction analysis and TGA analysis where HL is bis-[(E)-N′-(phenyl(pyridin-2-yl)methylene)]carbohydrazide. Single crystal X-ray analysis reveals that 1 has a Mn4 core in which Mn(II) ions are connected by azide and enolate oxygen atoms. IR spectroscopy and X-ray analysis indicate that the carbohydrazone is coordinated to the metal cores as a mononegative ligand in the enol form. The magnetic behavior of 1 was investigated between 2 and 295 K and indicated that the magnetic coupling mediated via azide bridge is ferromagnetic whereas the enolate oxygen mediates antiferromagnetic coupling that leads to overall antiferromagnetic behavior.Synthesis, X-ray structure, TGA analyzes, magnetic and spectroscopic properties of azide bridged tetranuclear Mn(II) cluster with carbohydrazone based ligand is reported.Display Omitted
Keywords: Mn(II) complex; Magnetic studies; Crystal structure; Spectroscopic studies; TGA analysis;

Synthesis and photophysical properties of axially substituted silicon (IV) tetrapyrazinoporphyrazines by Jong min Park; Chang Young Jung; Cheol Jun Song; Jae Yun Jaung (64-66).
We successfully synthesized non-aggregated silicon (IV) tetrapyrazinoporphyrazines (SiPz) bearing bornane groups at their peripheral positions. The UV–vis spectra of the SiPz complexes maintained a strong and sharp Q-band, which is an archetypal characteristic of non-aggregated phthalocyanines, in various organic solvents. In addition, the extreme red emission of SiPz complexes 4a–4c under visible light in a neutral solution condition was observed. However, the SiPz complex (4d) with axial aniline groups had very low fluorescence quantum yields due to the quenching ability of the aniline group.Axially substituted silicon (IV) tetrapyrazinoporphyrazines bearing bornane groups at their peripheral positions have been reported. Detailed synthesis and optical properties have been described. The spectral properties were influenced by the type of axial substituents.Display Omitted
Keywords: Silicon tetrapyrazinoporphyrazine; Aggregation; Fluorescence quantum yield; Fluorescence quenching; Camphorquinone;

Synthesis and aggregation-induced emission of a pyrene decorated chiral BODIPY chromophore by Tao Tao; Shu-Rong Wang; Liang Chen; Hui Qiu; Jing Xu; Min-Dong Chen (67-70).
BODIPY chromophore with pyrene moieties was designed and synthesized successfully in the present paper. Optical results demonstrate that the pyrene-terminated dye 3 presents a bigger Stokes shift and slightly smaller fluorescence quantum yield in the red region than BODIPY dye 1 bearing no substituent at 2,6-positions. Dye 3 possesses absorption and emission maximum at 530 and 585 nm in THF solution, respectively. With the addition of different water volume fractions, the gradually bathochromic shifts are observed in the absorption and emission spectra, simultaneously. Under UV irradiation, the corresponding emission images of solutions/aggregates are visual, showing the aggregation-caused quenching effect of orange fluorescence. In addition, theoretic computational studies on related pyrene decorated chiral BODIPY compounds have also been carried out.The first 2,6-disubstituted pyrene-terminated BODIPY dye is reported. This material presents a strong orange fluorescence peak with the high quantum yield. With the addition of different water volume fractions, the gradually bathochromic shifts are observed in the absorption and emission spectra, simultaneously.Display Omitted
Keywords: BODIPY; Pyrene; Synthesis; Fluorescence; Aggregation-induced emission;

Slow diffusion in situ ruthenium/ligand reaction: Crystal structures, fluorescence and biological properties by S.B. Moosun; S. Jhaumeer-Laulloo; S.J. Coles; L.H. Blair; E.C. Hosten; M.G. Bhowon (71-76).
Promoted by RuCl3·3H2O coordination in the mixed solvent DMF/H2O, diverse in situ S–S bond reactions such as S–S bond scission and S-oxidation occurred in the disulfide ligand of 2,2′-dithiodibenzoic acid (dtdb) to yield the new sulfinato-benzoate ligand (sb). The X-ray analysis of complexes of [Ru(phen)2(sb)] (1) and [Ru(bipy)2(sb)·H2O] (2) revealed that in both complexes, the ruthenium ion was found to be in an octahedral geometry, coordinating to the sulfur atom, rather than the oxygen of sulfinate. The complexes were found to be active against the bacterial strains tested with MIC ranging from 14.3–261 μM. In addition, the metal complexes present strong DNA binding affinity constants in the major or minor grooves at the order of magnitude 105-106  M− 1. The antioxidant activities of the ligand and its metal complexes were investigated through scavenging effects for DPPH in vitro, indicating that the compounds show stronger activities than some standard antioxidants, such as ascorbic and vitamin C.The reaction of 2,2′-dithiodibenzoic acid with RuCl3·3H2O in the presence of 1,10-phenanthroline and 2,2′-bipyridine under slow diffusion conditions led to the formation of an in situ generated sulfinato-benzoate ligand, prior to coordination with Ru. Both mononuclear complexes were in an octahedral environment, surrounded by carboxylate oxygens, sulfur atoms and nitrogen atoms of N-donor ligands. The biological and fluorescent properties of the compounds were evaluated.Display Omitted
Keywords: 2,2′-dithiodibenzoic acid; S-oxidation; Ruthenium; Bacterial strains; DNA binding; Antioxidant;

A high-nuclearity [Cu6Cd4] antiferromagnet with a supertetrahedral configuration by Xiao-Qing Zhao; Jin Wang; Dong-Xu Bao; Shuo Xiang; Dai-Bing Luo (77-80).
A heterometallic coordination cluster with the formula of {[Cu6Cd4(HL)4(piv)8(H2O)6]·4MeOH} (1, H4L = pentaerythritol, Hpiv = pivalic acid) has been synthesized. Compound 1 crystallizes in the tetragonal space group I-4, and consists of a supertetrahedral cage with four Cd(II) and six Cu(II) ions held together by μ 3-O bridges. Magnetic susceptibility exhibits that compound 1 is an antiferromagnet.A high-nuclearity mixed d-metal cluster based on pentaerythritol (H4L), consisting of a supertetrahedral [Cd4Cu6] cage, has been synthesized and characterized and suggests to be an antiferromagnet.Display Omitted
Keywords: Pentaerythritol; Heterometallic coordination cluster; Supertetrahedral cage; Antiferromagnet;

A new 3D metal–organic framework with pcu topology {[Cu2(TPOM)(ddpa)2]} n (1) was synthesized under solvothermal condition by employing flexible tetrakis(4-pyridyloxymethylene) methane (TPOM) and semirigid 4,4′-dicarboxydiphenylamine (H2ddpa) as well as Cu(II) ion. Complex 1 exhibits good endurance in acid/base aqueous solutions and a high catalytic activity for the reduction of 4-nitrophenol in excess NaBH4 solution.A new 3D metal–organic framework with pcu framework was synthesized by employing flexible tetrakis(4-pyridyloxymethylene)methane (TPOM) and semirigid 4,4′-dicarboxydiphenylamine (H2ddpa) as well as Cu(II) ion. In complex 1, TPOM shows a rare two coordinated mode. Complex 1 exhibits excellent endurance in acid/base aqueous solutions and a good catalytic activity for the reduction of 4-nitrophenol in excess NaBH4 solution.Display Omitted
Keywords: Metal–organic framework; Semirigid ligand; Stability;

The structures and dielectric properties of high temperature phase transition compounds with 4-(dimethylamino)pyridinium by Hui-Ting Wang; Qiang Li; Ping-Ping Shi; Lin Zhou; Yi Zhang; Qiong Ye; Da-Wei Fu (85-90).
The reactions of 4-(dimethylamino)pyridine (DMAP) and metal chloride in dilute hydrochloric acid yield two four-coordinate complexes, 1 (DMAP+)(FeCl4 ) and 2 (DMAP+)2(CoCl4 2 −). The differential scanning calorimetry (DSC) measurements, temperature-dependent dielectric properties and variable-temperature single-crystal X-ray diffraction analyses of compound 1 confirmed the reversible isostructural phase transition with the same space group P21/n (No. 14) at 298 K and 373 K. The temperature-dependent single crystal structural analyses of compound 1 reveal the distinct and synchronous molecular motions of both the cationic and anionic moieties, where the orientational changes of organic cations and the order–disorder transformations of FeCl4 anions are mainly responsible for dielectric properties of compound 1. The variable-temperature structure analyses and the variable-temperature PXRD measurements reveal that compound 2 undergoes a reversible structural phase transition at around 381 K. The space groups of compound 2 change from triclinic P-1 in room temperature phase (RTP) to monoclinic C2/c in high temperature phase (HTP), accompanied by thermal and dielectric anomalies.The two four-coordinate complexes, 1 (DMAP+)(FeCl4 ) and 2 (DMAP+)2(CoCl4 2 −), and their temperature-dependent crystal structures and dielectric properties have been synthesized and investigated. The orientational motions of organic cations and order–disorder transformations of FeCl4 anions result in the significant changes of the hydrogen bonds, however, with no change in the space group. In addition, the piezoelectric and SHG measurements were performed on compound 1 to further confirm the same centrosymmetric space group in both room and high temperature phases. Compound 2 undergoes a reversible structural phase transition at around 381.0 K. Their structural changes are reflected in the reversible dielectric transitions.DSC and dielectric analyses of 1 and 2 confirm the phase transitions at 360.0 K and 381.0 K, respectively.Display Omitted
Keywords: Phase transition; Orientational changes; Order–disorder; Differential scanning calorimetry; Dielectric; Variable-temperature X-ray;

Facile synthesis and molecular structure of the tris(amine) complex [PdCl(H2NBz)3]Cl·H2O by Subhi A. Al-Jibori; Wisam J. Hameed; Lamaan J. Al-Hayaly; Sucharita Basak-Modi; Graeme Hogarth (91-93).
Reaction of Na2[PdCl4] with three equivalents of benzylamine at room temperature led to the isolation of [PdCl(H2NBz)3]Cl·H2O in near quantitative yield, a rare example of a tris(monoamine)functionalised palladium(II) centre. A crystal structure showed that the three phenyl groups lie on the same side of the PdN3Cl plane and the metal-bound chloride is hydrogen bonded to the co-crystallised water.Reaction of Na2[PdCl4] with three equivalents of benzylamine led to the isolation of [PdCl(H2NBz)3]Cl·H2O in near quantitative yield, a rare example of a tris(monoamine)functionalised palladium(II) centre.Display Omitted
Keywords: Palladium; Benzylamine; Tris-substitution; Crystal structure; Hydrogen bonding;

Five rare earth complexes with 8-hydroxyquinoline derivatives as ligands were synthesized and characterized. The starting ligand L1 undergoes in situ ligand transformation in the formation of the complexes 14. Complexes 15 display binuclear structures. Complexes 1 and 5 exhibit luminescence that are similar with ligand. Magnetic studies indicate that 3 shows slow magnetic relaxation with the effective anisotropy barrier (ΔE/k B  = 30.9 K).Reaction of RE(dbm)3  ∙ 2H2O (RE = Y, Tb, Dy, Ho) and 8-hydroxyquinoline derivative ligands in different solvents resulted in five rare earth complexes. Complex 3 shows SMM behavior and is a novel 8-hydroxyquinoline-based Dy2 SMM.Display Omitted
Keywords: 8-hydroxyquinoline derivative; Rare earth complex; Binuclear; Single-molecule-magnet;

An unprecedented twelve-connected 3D metal-organic framework based on heptanuclear cobalt cluster building blocks by Li-Li Liang; Lei Xu; Yan-Chun Xue; Fei-Jian Chen; Hong-Bin Du (98-102).
Solvothermal reaction of flexible tetrapodal linker tetrakis[4-(carboxyphenyl) oxamethyl]methane acid (H4L) with cobalt salt yields a new metal-organic framework [Co7(L)3(μ 3-O)3(DMF)3]∙(DMF)13(H2O)25. X-ray crystallography reveals that the structure exhibits a unique 2-nodal (4,12)-connected topology with the Schläfli symbol of (433.630.83)(46)3, constructed from heptanuclear cobalt clusters as 12-connected nodes and tetrahedral ligands as 4-connected nodes. Temperature-dependent magnetic susceptibility measurements reveal that the heptanuclear cobalt clusters exhibit antiferromagnetic property.An unprecedented twelve-connected 3D metal-organic framework [Co7(L)3(μ 3-O)3(DMF)3]·(DMF)13(H2O)25 has been synthesized and characterized, which contains disk-like heptanuclear cobalt clusters as 12-connected nodes and tetrahedral ligands as 4-connected nodes. The structure exhibits a unique 2-nodal (4,12)-connected topology with the Schläfli symbol of (433.630.83)(46)3. Temperature-dependent magnetic susceptibility measurements reveal that the heptanuclear cobalt clusters exhibit antiferromagnetic property.Display Omitted
Keywords: Metal-organic framework; Heptacobalt cluster; Tetrakis[4-(carboxyphenyl)oxamethyl]methane acid; (4,12)-connected topology;

Six novel photoluminescent Ln–Cu(I) heterobimetallic 3D coordination polymers, [LnCu (pyip2 −)2(H2O)]n (16) (where Ln is Pr, Nd, Sm, Eu, Gd, Ho, respectively, and H2pyip = 5-(4-pyridyl) isophthalic acid) have been synthesized in a concise and reproducible manner under hydrothermal conditions. All of these substances were fully characterized by appropriate spectroscopic methods and elemental analysis. Structural determinations revealed that 16 are isomorphic and display 3D frameworks. Luminescent properties of the obtained compounds have been studied in detail revealing light emissions of warm white, cool white and light blue for 3, 4 and 5, respectively. The effectiveness of association of a rare earth with a transition metal in producing valuable luminescent materials for practical applications is demonstrated.Six novel coordination polymers namely [LnCu (pyip2 −)2(H2O)]n (Ln = Pr, Nd, Sm, Eu, Gd, Ho); (H2pyip = 5-(4-pyridyl) isophthalic acid) have been synthesized and their luminescent properties explored.Display Omitted
Keywords: Heterobimetallic coordination polymers; Crystal structure; Luminescent materials;

Synthesis, crystal structures and gas adsorption of two porous pillar-layered MOFs decorated with different functional groups by Xiao-Li Yan; Shu-Ni Li; Yu-Cheng Jiang; Man-Cheng Hu; Quan-Guo Zhai (107-110).
Take advantage of the readily accessible layered Zn-1,2,4-triazolate motif and two isometric dicarboxylate ligands with different functional groups (trans,trans-1,3-butadiene-1,4-dicarboxylic acid, TTBDC and 2,5-dihydroxyterephthalic acid, DOBDC), we report herein two porous Zn-triazolate-dicarboxylate pillar-layered MOFs. Flexible TTBDC led to the formation of MOF 1 crystallizing in Pna21 space group, but rigid DOBDC produced MOF 2 in P4/ncc space group. Both pillar-layered MOFs show not only remarkable H2 and CO2 uptake capacity, but also high CO2 over CH4 selectivity.Two microporous Zn-triazolate-dicarboxylate pillar-layered MOFs decorated with different functional groups exhibit not only remarkable H2 and CO2 uptake performance but also high CO2/CH4 selectivity.Display Omitted
Keywords: Pillar-layered MOFs; 1,2,4-triazole; CO2 uptake; CO2/CH4 selectivity;

pH dependent synthesis of structurally diverse praseodymium(III) coordination polymers based on isomeric ligands by Qi Wu; Meng Jie Cao; Bo Wei; Yu Bai; He Tian; Jing Wang; Qiao Liu; Qiao Yun Li; Gao Wen Yang (111-114).
Reactions of two isomeric ligands, 5-(n-pyridyl)tetrazole-2-acetato potassium salt (Kn-pytza, n = 2,4) and PrCl3·6H2O under solvothermal conditions, afforded three new complexes, [Pr(2-pytza)(SO4)(H2O)3]·H2O(1), [Pr(4-pytza)3(H2O)2]·2H2O (2) and [Pr4(4-pytza)5(OH)4(H2O)7Cl]Cl2·4H2O (3), whose structures are controlled by not only the different positions of the nitrogen atom of the pyridine ring but also the pH value of the solvent system. These compounds have been characterized by elemental analysis, IR and single crystal X-ray diffraction. The X-ray analysis reveals that compound 1 is a two dimensional layer structure made up of a Pr2O6 binuclear unit and the tridentate bridging SO4 2 − ligand; compound 2 is an unusual one dimensional ladder like chain structure consisting of a Pr2O10 binuclear unit and 4-pytza which acts as a tetradentate ligand via the pyridine-N and the carboxylate group in a μ 1,1,3-COO bridging mode while compound 3 is an unprecedented two dimensional network composed of a tetranuclear cubane-shaped Pr4(OH)4 8 + cluster (SBU) and tridentate 4-pytza via the pyridine-N and the carboxylate group in a μ 1,3-COO bridging mode. Various hydrogen bonds exist to assemble the 1D chains or 2D layers into 3D supramolecular network structures. Furthermore, the luminescence properties investigated at room temperature in the solid state show only intraligand emission for 1 and both intraligand and characteristic peaks of Pr3 + for either compound 2 or 3.Three novel praseodymium coordination compounds based on isomeric ligands 5-(n-pyridyl)tetrazole-2-acetato potassium salt (n = 2,4) have been successfully prepared, whose structures are controlled by not only the different positions of the nitrogen atom of the pyridine ring, but also the pH values. The luminescence shows ligand centered emission or both intraligand emission and characteristic peaks of Pr3 +.Display Omitted
Keywords: pH; Isomer; Pr(III); Crystal structure; Luminescence;

A novel phenolato- and peroxo-bridged dinuclear cerium(IV) complex, [Ce2L1L22-O2)]·(O3SCF3), where L1 and L2 are the deprotonated form of tris(2-((4-bromosalicylidene)amino)ethyl)amine and bis-(2-((4-bromosalicylidene)aminoethyl))(2-aminoethyl)amine, respectively, was prepared and characterized. The asymmetric unit of the complex contains a dinuclear cerium(IV) complex cation and a trifluoromethanesulfonate anion. The complex has effective activities against the bacteria Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas fluorescens.A novel dinuclear cerium(IV) complex was prepared. The complex has been characterized by single crystal X-ray diffraction. The complex has effective antibacterial activity.Display Omitted
Keywords: Schiff base; Cerium; Synthesis; Crystal structure; Antibacterial activity;