Inorganic Chemistry Communications (v.64, #C)

Contents List (iii-viii).

Crystal structure and chirality of adenosine-5′-diphosphate coordination complex by Pei Zhou; Chong Wang; Rufei Shi; Chuanfang Sheng; Hui Li (1-4).
The first neutral coordination complex of adenosine-5′-diphosphate (ADP) with transition metal Cu(II) ion, [Cu(phen)(H2ADP)(NO3)]·H2O (ADP–Cu) (ADP = adenosine-5′-diphosphate, phen = 1, 10-phenanthroline monohydrate) has been synthesized and investigated by X-ray single-crystal diffraction method. Based on its crystal structure and supramolecular assembly analysis, the molecular and supramolecular chirality of ADP–Cu was studied comprehensively by liquid- and solid-state circular dichroism (CD) spectroscopy. It is the first example of the study about the chirality and supramolecular chirality for polyphosphate nucleotide coordination complex.The chirality and supramolecular chirality for polyphosphate nucleotide coordination complex was studied based on single crystal structure analysis combined with liquid and solid state circular dichroism (CD) spectroscopy for the first time.Display Omitted
Keywords: Polyphosphate nucleotide complex; Single crystal structure; Supramolecular assembly; Chirality; Solid-state circular dichroism spectroscopy;

The cluster complex (C5H5)4Fe4S4 formally contains Fe(III) and sulfide as constituents. In agreement with this assignment, the long-wavelength absorptions of the cluster are attributed to S2 − to Fe(III) LMCT transitions. In solutions of acetonitrile, LMCT excitation of the cluster complex leads to a photoredox decomposition yielding Fe(II) and elemental sulfur. Upon a one-electron oxidation of (C5H5)4Fe4S4, the cation [(C5H5)4Fe4S4]+ is obtained, which is much more stable to water, air and light than the neutral parent cluster. Upon addition of [M(CN)6]4 − with MRu and Os to aqueous solutions of this cation, dark blue and violet colors, respectively, immediately develop, which are attributed to outer-sphere CT absorptions of the ion pairs [(C5H5)4Fe4S4]+/[M(CN)6]4 −.The cluster complex Cp4Fe4S4 undergoes a photoredox photolysis upon sulfide to iron(III) LMCT excitation yielding ferrocene, Fe2 +, sulfide and elemental sulfur.Display Omitted
Keywords: Iron sulfur cluster; Photochemistry; CT transitions;

Studies on the bioactivities of 8-mercaptoquinoline sulfide derivatives by Jing-An Zhang; Li-Jie Zhang; Xun-Zhong Zou; Ya-Jie Liu; Wei Gao; Yu Li (7-12).
This review gives a brief overview on bioactivities of 8-mercaptoquinoline sulfide derivatives involving antimicrobial activity, anticancer activity, inhibitors as well as other activities. Special emphasis is given to the most recent examples.Display Omitted
Keywords: 8-Mercaptoquinoline; Sulfide; Bioactivities;

A tris-diketonate-Eu(III) complex with the brominated 2,2′-bpy ancillary ligand doped in PMMA for high color-purity red luminescence by Yani He; Lin Liu; Zhao Zhang; Guorui Fu; Xingqiang Lü; Wai-Kwok Wong; Richard A. Jones (13-15).
Through the physical doping of a new red-emitting (Ф Eu L  = 34.9%) tris-β-diketonate Eu3 +-complex [Eu(DBM)3(5-Br-2,2′-bpy)] (1; DBM = dibenzoylmethane) with the brominated 2,2′-bpy ancillary ligand 5-Br-2,2′-bpy (5-bromo-2-(pyridin-2-yl)pyridine) in PMMA (poly(methyl methacrylate), the obtained hybrid material 1@PMMA exhibits significantly improved physical properties including the enhanced Eu3 +-based color-purity red luminescence (Ф Eu L  = 53.7%).Based on the doping of a tris-β-diketonate Eu3 +-complex [Eu(DBM)3(5-Br-2,2′-bpy)] (1) with the bromination-modified 5-Br-2,2′-bpy in PMMA, the obtained hybrid material 1@PMMA exhibits significantly improved physical properties including the enhanced Eu3 +-based color-purity red emissions (Ф Eu L  = 53.7%).Display Omitted
Keywords: Tris-β-diketonate Eu3 +-complex; Heavy-atom effect; PMMA-supported doping material; High color-purity red luminescence;

A novel cadmium metal organic framework, {[Cd(L)(H2O)]∙THF}n (1), has been synthesized solvothermally using a newly synthesized ligand (L = 4-(((1 H-imidazol-2-yl)methylene)amino)benzoic acid). Complex 1, is a 3D supramolecular framework having 2D hydrogen bonded undulated sheets. The network contains solvent accessible void volume of 34.0% which is occupied by THF solvent molecules. The compound exhibits a (4,4) connected binodal network. Solid state photo luminescent property of 1 in different solvents has also been investigated which demonstrate distinct solvent dependent luminescent spectra.A conjugated schiff base derived novel 4,4-c connected binodal porous 2D metal–organic framework was synthesized and characterized by single crystal XRD. The open voids were filled up with THF solvent molecules. Solid state photo luminescent property in different solvents shows distinct solvent dependent luminescent spectra at room temperature.Display Omitted
Keywords: Solvothermal; Cadmium(II); Metal–organic framework; Topology; Emission;

In this work, one new porphyrin, 5, 10, 15, 20-tetrakis(4-N-pyrazolyl)phenyl porphyrin (H2Pp) was synthesized and characterized. The single crystal structures of H2Pp and its cobalt(II) porphyrin (Co(II)Pp) were obtained with a space group of P 1 and I2/c, respectively. The porphyrin macrocycle is close to a perfect plane in H2Pp, while Co(II)Pp exhibits a saddle-type distortion due to the formation of shorter Co–N coordination bonds. In H2Pp, the molecules are interconnected through π⋯π and C–H⋯π interactions to form 3D architecture, while in Co(II)Pp the porphyrin molecules are interlinked only by C–H⋯π interactions to yield 3D structure. We examined the UV–vis spectra and fluorescent spectra of H2Pp and Co(II)Pp in CH2Cl2 and solid state at room temperature. In addition, the catalytic activities of Co(II)Pp to the ethylbenzene oxidation was examined, the results indicate that Co(II)Pp exhibits a high selectivity to acetophenone (> 99%) with the conversion of 83%.In H2Pp, the molecules are interconnected through π⋯π and C–H···π interactions to form 3D structure, while in Co(II)Pp the porphyrin molecules are interlinked only by C–H⋯π interactions to yield 3D structure. Co(II)Pp displays high catalytic activity with the only product acetophenone quantitatively in 83%.Display Omitted
Keywords: Porphyrin; Cobalt(II) porphyrin; Crystal structure; Catalytic oxidation;

Synthesis and structural characterization of copper(II) coordination polymers with 1,1,2,2-tetra(pyrazol-1-yl)ethane by Evgeny Yu. Semitut; Vladislav Yu. Komarov; Evgeny Yu. Filatov; Anastasia S. Kuznetsova; Andrei I. Khlebnikov; Andrei S. Potapov (23-26).
Reaction between 1,1,2,2-tetra(pyrazol-1-yl)ethane (Pz4) and copper(II) nitrate in ethanol at room temperature and in solvothermal conditions (90 °C) lead to coordination polymers of two different structures. A ribbon-like coordination polymer {Cu22-NO3)2(H2O)4  μ′2-Pz4}n was formed at room temperature in which nitrate ions bind the monomeric units, while Pz4 ligands are responsible for cross-linking of {Cu(μ-NO3)} chains. At 90 °C linear 1D coordination polymer was formed, in which Pz4 ligands bridge copper ions that in addition bear two monodentate nitrate ions.Two new copper(II) coordination polymers with bitopic ligand 1,1,2,2-tetra(pyrazol-1-yl)ethane were prepared and their crystal structure was determinedDisplay Omitted
Keywords: Bis(pyrazol-1-yl)methane; 1,1,2,2-tetra(pyrazol-1-yl)ethane; Copper(II) nitrate; Bitopic ligand; Coordination polymers; Crystal structure;

Binuclear cyano-bridged complex derived from [MnIII(salpn)] and [FeIII(CN)6]: Synthesis, structure and magnetic properties by Vyacheslav A. Kopotkov; Denis V. Korchagin; Artem D. Talantsev; Roman B. Morgunov; Eduard B. Yagubskii (27-30).
The reaction of the neutral [Mn(salpn)C(CN)3(H2O)] (salpn2 −  =  N,N -1,3-propylenebis(salicylideneiminato) dianion) with [FeIII(CN)6]3 − in the presence of strong oxidizer (NH4)2S2O8 yields a binuclear anion complex [NH3CH2CH2CH2NH3]2 +{[MnIII(salpn)(H2O)][FeIII(CN)6]}2 − (1). Its structure, DC and AC susceptibility have been studied. Frequency dependence of the AC susceptibility characteristic for single-molecule magnets has been found.Binuclear anion complex {[MnIII(salpn)(H2O)][FeIII(CN)6]}2 −[NH3CH2CH2CH2NH3]2 + was synthesized as the product of reaction between [Mn(salpn)C(CN)3(H2O)], K3[Fe(CN)6 and (NH4)2S2O8. Its structure and magnetic properties were studied. The complex shows slow magnetic relaxation characteristic of single-molecule magnets.Display Omitted
Keywords: Magnetic properties; Manganese(III); Hexacyanoferrate(III); Cyano-bridged; Single-molecule magnets;

Constructing two new crystalline metal–organic frameworks based on a mixed-donor ligand by Xiaofang Wang; Ming Xue; Gang Wu; Ying Pan; Shilun Qiu (31-34).
The self-assembly of a prominent ligand, 5-(4-(1H-tetrazolyl)phen)isophthalic acid (H3TZPI), with Zn2 +/Cu2 + centres generates two new MOFs, [Zn2(TZPI)(μ 3-OH)(H2O)2]·2H2O (JUC-161) and [Cu(HTZPI)(μ 2-H2O)0.5(H2O)1.5]·5(H2O) (JUC-162). JUC-161 exhibits fascinating three-dimensional structures containing rectangular channels with dimensions of 6.5 × 3.0 Å2, and JUC-162 displays 3D supramolecular structures with 12.5 × 14.6 Å2 hexagonal channels. The observed structural diversity in these frameworks is due to the two distinct coordinating moieties of the H3TZPI ligand. The photoluminescence of JUC-161 and the magnetic properties of JUC-162 are also measured at room temperature. Photoluminescence investigations reveal that JUC-161 displays a strong main emission spectrum peak at 388 nm. JUC-162 is found to exhibit an antiferromagnetic interaction between Cu2 + ions.The self-assembly of one prominent ligand, 5-(4-(1H-tetrazolyl)phen)isophthalic acid (H3TZPI), with Zn2 +/Cu2 + centres generates two new MOFs named JUC-161 and JUC-162 (JUC = Jilin University, China). Due to the rotation of different motifs in the ligand and its varied coordination modes, JUC-161 and JUC-162 exhibit fascinating 3D frameworks containing distinct channels. The fluorescence property of JUC-161 and the magnetic property of JUC-162 indicate that these MOFs may be good candidates for multifunctional materials.Display Omitted
Keywords: Metal–organic frameworks; Configurations; Luminescence; Magnetism;

The aldimine and ketimine forms of two Schiff base complexes formed by the condensation of two isomeric imidazole carboxaldehydes with an amino acid are reported. Reaction of L1, the Schiff base condensate of 5-methyl-4-imidazolecarboxaldehyde (5Me4Im) and valine, with copper(II) perchlorate results in the isolation of [Cu(L1)(5Me4Im)(ClO4)] while the analogous reaction of L2, the Schiff base condensate of 1-methyl-2-imidazolecarboxaldehyde (1Me2Im) with alanine, and nickel(II) results in the isolation of [Ni(L2)2]. L1 exhibits the expected aldimine form of the amino acid derived Schiff base, 5Me4Im-CH = N-CH(R)CO2 , while L2 exhibits the tautomeric ketimine form, 1Me2Im-CH2–N = C(R’)CO2 . Structural data clearly support the two tautomeric forms. The ketimine form, observed in [Ni(L2)2], has been proposed as an intermediate in the racemization and transamination of amino acids.Equilibrium of aldimine and ketimine forms of amino acidDisplay Omitted
Keywords: Aldimine; Ketimine; Amino acid metal complex; Amino acid racemization; Amino acid transmination; Amino acid ketimine metal complex;

Synthesis, characterisation and cytotoxicity studies of Manganese(I) and Rhenium(I) based metallacrown ethers by Chowan Ashok Kumar; R. Nagarajaprakash; W. Victoria; V. Veena; N. Sakthivel; Bala. Manimaran (39-44).
Manganese(I) and Rhenium(I) based metallacrown ethers [M(CO)3Br(μ-pcatgd)] (1, M = Mn; 2, M = Re) were synthesised by the reaction of M(CO)5Br (M = Mn, Re) and pyridine appended bidentate ligand crafted with flexible polyether spacer. The self-assembled mononuclear compounds 1 and 2 were characterised by IR, NMR, UV–Visible absorption and emission spectroscopic techniques. Molecular structure of 2 was determined by single-crystal X-ray diffraction methods and the molecular masses of 1 and 2 were confirmed by ESI–mass spectrometry. Anticancer activities of compounds 1 and 2 were investigated by in vitro cytotoxicity studies against different cancer cell lines as well as on normal cells. Compounds 1 and 2 showed a broad-spectrum inhibition on few cancer cells that were comparable to cisplatin. Compound 1 exhibited selective inhibition of cancer cells upon irradiation at λ max 365 nm in dose-dependent manner. Morphological studies showed the induction of apoptosis in compound 1-treated cancer cells upon irradiation. The UV–Visible absorption spectroscopy-based myoglobin assay further supported the nature of compound 1 as photoactivatable CO releasing molecule (PhotoCORM).Manganese(I) and Rhenium(I) based metallacrown ethers [M(CO)3Br(μ-pcatgd)] (1, MMn; 2, MRe) were synthesised by the reaction of M(CO)5Br and pyridine appended polyether spacer. Compounds 1 and 2 showed a broad-spectrum inhibitory activity on few cancer cells comparable to a reference compound (cisplatin).Display Omitted
Keywords: Self-assembly; Manganese/rhenium; Metallacrown; Anticancer activity;

A novel copper(II) complex identified as a potent drug against colorectal and breast cancer cells and as a poison inhibitor for human topoisomerase IIα by Shayna Sandhaus; Rosella Taylor; Tiffany Edwards; Alexis Huddleston; Ykeysha Wooten; Ramaiyer Venkatraman; Ralph T. Weber; Antonio González-Sarrías; Patrick M. Martin; Patrice Cagle; Yuk-Ching Tse-Dinh; Stephen J. Beebe; Navindra Seeram; Alvin A. Holder (45-49).
A novel complex, [Cu(acetylethTSC)Cl]Cl·0.25C2H5OH 1 (where acetylethTSC = (E)-N-ethyl-2-[1-(thiazol-2-yl)ethylidene]hydrazinecarbothioamide), was shown to have anti-proliferative activity against various colon and aggressive breast cancer cell lines. In vitro studies showed that complex 1 acted as a poison inhibitor of human topoisomerase IIα, which may account for the observed anti-cancer effects.A novel copper(II) complex is shown to be a topoisomerase II poison that displays significant anti-cancer effects.Display Omitted
Keywords: Thiosemicarbazones; Copper(II); Human topoisomerase Iiα; Breast cancer; ESR spectroscopy; Cyclic voltammetry;

1,3-alternate conformation of a gallium calix[4]arene based on a benzimidazolyl ligand by Nazario Lopez; Ernesto Rufino-Felipe; Miguel-Ángel Muñoz-Hernández (50-52).
Synthetic and structural studies on a tetrameric metalla [4]calixarene [tmbzimGaMe2]4 with 1,3 alternate conformation were carried out in this work (tmbzim: 2,5,6-trimethylbenzimidazolate). Multiple intermolecular interactions prevent the expected formation of inclusion complexes with small aromatic guests.Synthetic and structural studies on a tetrameric metalla[4]calixarene [tmbzimGaMe2]4 with 1,3 alternate conformation were carried out in this work (tmbzim: 2,5,6-trimethylbenzimidazolate). Multiple intermolecular interactions revent the expected formation of inclusion complexes with small aromatic guests.Display Omitted
Keywords: Metallacalixarenes; Metallacycles; Gallium; Benzimidazolyl;

A square planar nickel(II) complex derived from a unique metal ion-promoted transformation of 2-benzoylpyridine by Alexandros A. Kitos; Dimosthenis P. Giannopoulos; Constantina Papatriantafyllopoulou; Luís Cunha-Silva; Spyros P. Perlepes (53-55).
A novel metal ion-mediated reaction of 2-benzoylpyridine in acetonitrile under strongly basic conditions has led to a 1:2 square planar Ni(II) complex containing the anion of 3-hydroxy-3-phenyl-(3-pyridin-2-yl)propanenitrile as ligand; the complex has been characterized by single-crystal X-ray crystallography and various spectroscopic techniques.A unique NiII-assisted transformation of 2-benzoylpyridine has been observed in MeCN under basic conditions resulting in an interesting square planar nickel(II) complex.Display Omitted
Keywords: 2-benzoylpyridine; Crystal structure; 3-hydroxy-3-phenyl-(3-pyridin-2-yl)propanenitrile; Ligand field spectrum; Metal ion-assisted ligand's transformation; Square planar nickel(II) complex;

Synthesis, structures, and photoluminescent properties of two uranium complexes constructed by a flexible zwitterion ligand by Lingling Liang; Ronglan Zhang; Ng Seik Weng; Jianshe Zhao; Chiyang Liu (56-58).
Two novel uranium complexes were constructed by using a tripodal flexible zwitterion ligand 1,1′,1″-(2,4,6-trimethylbenzene-1,3,5-triyl)-tris(methylene)-tris(pyridine-4-carboxylic acid) trichlorine (H3LCl3). Reaction of uranyl acetate dihydrate and H3LCl3 in aqueous solution affords (UO2)4L2Cl4(μ 3-O)2 .4H2O (1), which contains tetranuclear motifs, resulting in the two dimensional structure. UO2L2 .2NO3 .H2O (2) obtained via the reaction of H3LCl3 and uranyl nitrate hexahydrate, which displays a three dimensional structure. The structures were detected by single crystal X-ray crystallography, elemental analysis (EA), infrared (IR) spectroscopy, and thermogravimetric analysis (TGA). Furthermore, luminescent properties were also investigated.Two novel uranium complexes were constructed by using 1,1′,1″-(2,4,6-trimethylbenzene-1,3,5-triyl)-tris(methylene)-tris(pyridine-4- carboxylic acid) trichlorine (H3LCl3) as the ligand for the first time.Display Omitted
Keywords: Uranium complex; Photoluminescent property; Flexible zwitterion ligand;

Two novel coordination polymers, [Cd2(cdc)2(bmis)2] (1) and [Zn6(cdc)4(OH)4(bmis)4]·2H2O·4DMF (2) (bmis = bis(4-(2′-methylimidazol-ylphenyl)sulfone, H2cdc = 1,4-cyclohexanedicarboxylic acid), have been synthesized and structurally characterized. Compound 1 features an interesting usf net presenting the alternate arrangement of the single- and triple-stranded helices. Compound 2 exhibits an unusual two-fold interpenetrating polyrotaxane motif composed of two interlocked sets of identical pcu nets. In addition, their photoluminescent properties have also been evaluated.Two novel coordination polymers, [Cd2(cdc)2(bmis)2] (1) and [Zn6(cdc)4(OH)4(bmis)4]·2H2O·4DMF (2) (bmis = bis(4-(2′-methylimidazol)phenoxy)methane, H2cdc = 1,4-cyclohexanedicarboxylic acid), have been synthesized and structurally characterized. Compound 1 features an interesting usf net presenting the alternate arrangement of the single- and triple-stranded helices. Compound 2 exhibits an unusual two-fold interpenetrating polyrotaxane motif composed of two interlocked sets of identical pcu nets.Display Omitted
Keywords: Coordination polymers; Helice; Polyrotaxane; Luminescence;

Graphene oxides doped MIL-101(Cr) as anode materials for enhanced electrochemistry performance of lithium ion battery by Gaihua Li; Fengcai Li; Hao Yang; Fangyi Cheng; Na Xu; Wei Shi; Peng Cheng (63-66).
MIL-101(Cr)/graphene oxides composites has been successfully synthesized via a facile route using a solvothermal treatment and fully characterized using powder X-ray diffraction (PXRD), scanning electron microscope (SEM), thermal gravimetric analysis (TGA) and infrared spectroscopy (IR). The specific capacity of MIL-101(Cr)/GO are almost twice larger than that of MIL-101(Cr) at the first discharge process and the multiple relationship maintained over 40 cycles, indicating that the electrochemical performance of MIL-101(Cr) as anode material has been improved through doping by GO.MIL-101(Cr)/graphene oxide composites have been successfully synthesized via a facile route using a solvothermal treatment. The morphology of GO reveals typical fold lamellar structure and MIL-101(Cr) is octahedral crystal morphology distributed uniformly with size about 1 μm. The graphene oxide dispersed uniformly over MIL-101(Cr). The rate performance confirmed the enhancement of GO doping on electrochemical performance.Display Omitted
Keywords: MIL-101(Cr); MIL-101(Cr)/graphene oxides composites; Electrochemical performance;

The redox-active ligand 1-(2-pyridylazo)-2-acenaphthequinol (PAAL) and its zinc complex Zn(PAAL)2 were isolated and characterized by single crystal X-ray diffraction, 1H NMR, UV–Vis spectra and TGA, as well as their fluorescence and third-order nonlinear optical properties were preliminary investigated. The electronic structure of the complex is examined by cyclic voltammogram, while density functional theory calculations also support the redox-active nature of the PAAL ligand.The redox-active ligand 1-(2-pyridylazo)-2-acenaphthequinol (PAAL) and its zinc complex Zn(PAAL)2 were isolated and characterized by single crystal X-ray diffraction, 1H NMR, UV–Vis spectra and TGA, as well as their fluorescence and third-order nonlinear optical properties were preliminary investigated.Display Omitted
Keywords: Zinc complex; Fluorescence; Redox-active; DFT calculation;

Synthesis, structure and unprecedented self-assembly strategy of two six-membered Zn–organic macrocycles by Fei-Fei Zhu; Jie-Fang Fang; Yan-Ju Xiong; Qian Cheng; Yun Li; Shan-Tang Yue (71-73).
Two novel cyclohexane-like metallamacrocycles [ZnCH3COO(L)]6·solvent (1) and [Zn(HNO3)(L)]6·solvent (2) (HL = 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine) have been synthesized under hydrothermal conditions and characterized by IR spectra, single crystal X-ray diffraction, PXRD analysis, thermogravimetric analysis. The X-ray single crystal diffraction indicates that the self-assembly of the metallamacrocycle generates a fused-ring network that is further assembled into a 3D structure with 1D suprachannels. In particular, a designed self-assembly strategy has been applied to achieving six-membered Zn–organic metallamacrocycles unprecedentedly.3D supramolecular frameworks with 1D suprachannels generated by self-assembly based on supramolecular interactions of Zn–organic cyclohexane-like metallamacrocycles.Display Omitted
Keywords: Self-assembly; Metallamacrocycles; Strategy; Suprachannels;

Corrigendum to “Synthesis and structures of monocyclic 1,4-diaza-2,3-diborine species” [Inorganic Chemistry Communications 61 (2015) 214–216] by H. Can Söyleyici; Sultan Uyanık; Resul Sevinçek; Erkan Fırıncı; Banu Bursalı; Osman Burgaz; Muhittin Aygün; Yüksel Şahin (74-75).