Inorganic Chemistry Communications (v.51, #C)

Contents List (iii-xi).

Avoiding cross-linking in iron-polyphosphazene metallo-polymers by Ross J. Davidson; Eric W. Ainscough; Andrew M. Brodie; Mark R. Waterland; Harry R. Allcock; Mark D. Hindenlang; Guy N. L. Jameson (1-3).
Two new polyphosphazene ligands containing 1,10-phenanthrolin-2-olate (L1 ) and 2,2ʹ-bipyridine-6-olate moieties (L2 ) with 5,5ʹ-di-tert-butylbiphenyl-2,2ʹ-bis(olate) co-substituents were synthesised and then reacted with Fe(Pyridine)4(NCS)2. Variable temperature Mössbauer and electronic absorbance spectroscopies were used to establish the physical behaviour of the new iron-polyphosphazenes. By attaching two bidentate ligands to a geminal phosphorus atom a pseudo tetradentate ligand can be formed that prevents cross-linking when iron is coordinated to the polyphosphazene.Cross-linking in metallo-polyphosphazenes can be prevented by attaching two bidentate donors in a geminal fashion to the phosphorus atoms in the polymer chain.Display Omitted
Keywords: Metallo-polyphosphazene; Iron thiocyanate complex; Mӧssbauer spectroscopy; X-ray crystallography;

Synthesis, characterization and application of iron N-substituted imidazole complexes with the motif ClFeL4OFeCl3 by Peter Döhlert; Elisabeth Irran; Robert Kretschmer; Stephan Enthaler (4-8).
The activation of molecular oxygen was investigated applying a mixture of iron(II) chloride and N-substituted imidazole ligands. The resulting complexes were characterized and investigated by various techniques, pointing out bimetallic complexes with the general Cl(imidazole)4FeOFeCl3 motif. The complexes contain two different iron centers, on the one hand iron with an octahedral geometry and on the other hand iron with a tetrahedral geometry were observed. Both units are connected via a bridging oxido-ligand. Moreover, the complexes have been applied as precatalyst in iron-catalyzed epoxidation of stilbene.Display Omitted
Keywords: Iron; Nitrogen ligands; Oxygen activation; Catalysis; Epoxidation;

A 3D metal–organic framework (MOF), [Co33-OH)(μ2-H2O)(BPT)(HBPT)(DMF)2]·(DMF)(H2O) (1) (DMF = N, N′-dimethylformamide) has been synthesized by self-assembly of cobalt(II) oxide and biphenyl-3, 4′, 5-tricarboxylate (H3BPT) under solvothermal reaction. Compound 1 displays unique (2,3,10)-connected trinodal connected topology. Besides, 1 represents a rare example of MOF possessing free carboxylic acids. In addition, the magnetic property of the compound is investigated.A novel cobalt based MOF with intriguing topology has been synthesized and characterized by various state-of-the-art methods. It represents a rare example of MOF containing free carboxylic acids. In addition, the magnetic property of the compound is investigated.Display Omitted
Keywords: Metal–organic framework; Biphenyl-3, 4′, 5-tricarboxylate (H3BPT); Crystal structure; Free carboxylic acids; Antiferromagnetic interaction;

Copper(II) complexes derived from bidentate N,O-ligands for catalytic aerobic oxidation by Guoqi Zhang; Li Li; Chengxiong Yang; E. Liu; James A. Golen; Arnold L. Rheingold (13-16).
Two CuII complexes based on bidentate N,O-ligands have been synthesized and structurally characterized. X-ray structural analysis revealed that in complex 1 the CuII center adopts an unusual near tetrahedral coordination geometry, while the CuII core in 2 is traditionally square planar, albeit both of them have a N2O2 coordination environment and two compounds are mononuclear bis-ligand neutral complexes. A two-dimensional sheet-like network was observed in 2, resulting from the weak Cu…O contacts between the nitrato groups and axial CuII sites. Both complexes were tested for catalytic aerobic oxidation of benzylic alcohol and the results indicated that 2 was a better catalyst than 1. High yield of benzaldehyde was observed when using 2 as a catalyst in combination with TEMPO in an aqueous potassium carbonate solution at 60 °C.Two CuII complexes based on bidentate N,O-ligands have been synthesized and structurally characterized by X-ray diffraction analysis. The CuII centers in two complexes adopt different coordination geometries, and catalytic tests revealed that the complex with a traditional square-planar geometry CuII displayed much higher catalytic activity for the aerobic oxidation of benzylic alcohol than that having a nearly tetrahedral CuII core.Display Omitted
Keywords: N,O-ligand; Copper(II) complex; Crystal structure; Catalysis; Aerobic oxidation;

Unique 1D → 3D polycatenated architecture constructing from 1D single-armed chains incorporating with two rigid aromatic coligands by Wei Xia; Ping Tang; Xue-Qian Wu; Jian Cui; Dong-Sheng Li; Wen-Wen Dong; J.Y. Lu (17-20).
A new supramolecular architecture, {[Zn(FDC)(phen)(H2O)]·0.5H2O}n (1), was obtained from mixed rigid ligands [9-fluorenone-2,7-dicarboxylic acid (H2FDC), 1,10-phenanthroline (phen)] and zinc(II) nitrate under hydrothermal reactions, which displays a charming 1D → 3D polycatenated motif based on 1D single-armed polymeric chains via powerful π―π stacking interactions. In addition, the thermal stability and photoluminescence property of 1 were also investigated.A unique entangling Zn(II)-network shows a self-catenated π―π stacking topological structure, which can be viewed as the crosslink of 1D → 3D inclined polycatenated framework consisting of two of sets of 1D single-armed polymeric chains.Display Omitted
Keywords: Polycatenated motif; Zn(II) compound; 9-Fluorenone-2,7-dicarboxylate; Luminescent property;

Heteropolynuclear Schiff-base complexes Cu–Ln–Fe (Ln = Sm & Pr) with magnetic property by Dan-Dan Ding; Ting Gao; Ou Sun; Guang-Ming Li; Yu-Hong Wu; Miao-Miao Xu; Xiao-Yan Zou; Peng-Fei Yan (21-25).
Two new complexes [{CuL}Sm(H2O)3{Fe(CN)6}]2·6H2O (1) [{CuL}2Pr(H2O){Fe(CN)6}]2·4H2O (2) (H2L =  N,N′-ethylenebis(3-methoxysalicylideneimine)) have been prepared by reactions of acyclic compartmental Schiff-base heterodinuclear 3d–4f compound [{CuL}Ln(NO3)3] (Ln = Sm & Pr) with K3[Fe(CN)6]. Crystal structures of both 1 and 2 reveal unique topology structures. 1 shows a dimeric heterotrinuclear [{CuL}Sm(H2O)3{Fe(CN)6}]2 while 2 displays a dimeric heterotetranuclear [{CuL}2Pr(H2O){Fe(CN)6}] with distorted sandwich moieties [{CuL}2Pr]. Both 1 and 2 form similar 1D ladder-like structure through the intermolecular double bridges of Cu–N bonds. The measurement of variable-temperature magnetic susceptibility reveals that both complexes 1 and 2 exhibit antiferromagnetic interaction between spin carriers.Two heteropolynuclear Schiff-base complexes have been prepared by reactions of acyclic compartmental Schiff-base heterodinuclear 3d-4f compound [{CuL}Ln(NO3)3] with K3[Fe(CN)6]. Both complexes exhibit antiferromagnetic interaction between spin carriers.Display Omitted
Keywords: Heteropolynuclear; Schiff-base; 3d–4f–3d′; Dimeric; Magnetic property;

The dicarboxylic acid, 7,12-(COOH)2-CB11H10 , was prepared and characterized by NMR, IR, MS, and single-crystal X-ray diffraction. Titration studies reveal that 7,12-(COOH)2-CB11H10 has a pK a of > 6.35, indicating that this is a significantly weaker acid than typical organic carboxylic acids. This compound is the first example of a CB11 cluster with a B-COOH group to be characterized by X-ray diffraction and the only X-ray structure of a boron cluster that contains an adjacent pair of these groups.
Keywords: Carboranes; Boron clusters; Carboxylic acids; X-ray structure;

Two new indium coordination polymers (CPs) with mixed-ligand formulated as {[In(1,4-bda)1.5(phen)]·2H2O}n (In1) and {In(1,4-bda)(2,2′-bipy)Cl}n (In2) (1,4-H2bda = 1,4-benzenedicarboxylic acid; phen = 1,10-phenanthrolin; 2,2′-bipy = 2,2′-bipyridine) have been synthesized and characterized by single-crystal X-ray diffraction, infrared (IR), elemental analysis and thermal gravimetric analyses (TGA). In1 exhibits one-dimensional (1D) ladder chain, which further forms three-dimensional (3D) structure with π⋯π stacking interaction. Formation of 3D compact supramolecular framework in In2 is generated through C–H…Cl hydrogen bonding contacts and π⋯π stacking interaction. The photoluminescence (PL) characterizations to In1 and In2 affected by solvent and temperature are studied in detail. Thermogravimetric curves showed that In1 and In2 start to undergo phase transition until ca. 450 °C and 495 °C, respectively.Two new indium coordination polymers (CPs) with mixed-ligand formulated as {[In(1,4-bda)1.5(phen)]·2H2O}n (In1) and {In(1,4-bda)(2,2′-bipy)Cl}n (In2) (1,4-H2bda = 1,4-benzenedicarboxylic acid; phen = 1,10-phenanthrolin; 2,2′-bipy = 2,2′-bipyridine) have been synthesized under hydrothermal conditions. In1 exhibits one-dimensional (1D) ladder chain, which further forms three-dimensional (3D) structure by π⋯π stacking interaction. The 3D inserted compact supramolecular framework in In2 is generated through C–H⋯Cl hydrogen bonding contacts and π⋯π stacking interaction between neighboring 1D zigzag chains. The emission peak positions of In1 are sensitive to different polar solvents, assuming solvent-dependent PL. By contrast, the PL spectrum of In2 does not change in different solvents, and possesses better PL stability.Display Omitted
Keywords: Indium coordination polymers; Supramolecular framework; Photoluminescence; Thermogravimetric curves;

N-ferrocenyl isonicotinamide, a redox-active 1D hydrogen-bonded chain structure capable of supporting a mixed-valent redox state by Eric Patterson; Bryan Brautigam; William Farnsworth; McDonald Eric; Guang Wu; Stephen Contakes (36-39).
N-ferrocenyl isonicotinamide was prepared in 28% isolated yield by the acetylation of aminoferrocence with isonicotinoyl chloride in THF and 61% isolated yield by HOBt mediated DCC coupling in CH2Cl2 and characterized by NMR, IR, ESI-MS, and UV-vis spectroscopy. The structure of Nferrocenyl isonicotinamide, C16H14FeN2O, at 100 K exhibits orthorhombic (Pbca) symmetry. The N-ferrocenyl isonicotinamide's amide group is twisted by 31.7° with respect to the py group and 9.7° relative to the attached Cp ring, in contrast to the planar structure observed for the isomeric (4- Pyridylaminocarbonyl)ferrocene. Adjacent isonicotinamide groups form 1D hydrogen bonded chains through the amide CO and NH groups; this H-bonding network is oriented along the [010] direction. Solid state cyclic voltammetry indicates that this hydrogen bonding network is capable of supporting a class III mixed valent redox state. In contrast, CH2Cl2 and MeCN solutions of the complex exhibit a Fc+/0 redox potential of 420-430 mV vs. Ag/AgCl.The crystal structure of N-ferrocenyl isonicotinamide reveals that its amide group is twisted by 31.7° with respect to the py group and 9.7° to the Cp. Adjacent isonicotinamide groups form 1D hydrogen bonded chains through the amide. Solid state cyclic voltammetry indicates that the network can support a class III mixed valent redox state containing alternating Fc and Fc+ units.Display Omitted

The lowest energy (η5-C5H5)MoC3B8H11 structure is predicted to be a 12-vertex deltahedron with the molybdenum atom at a degree 7 vertex.The lowest energy (η5-C5H5)MoC3B8H11 structure is predicted to be a 12-vertex deltahedron with the molybdenum atom at a degree 7 vertex.Display Omitted
Keywords: Metallacarboranes; Molybdenum tricarbaborane; Non-icosahedral 12-vertex structures; Density functional theory;

A new flexible Salen-type dysprosium coordination polymer, e.g. {[Dy2(H2L)4Cl4(CH3OH)2]Cl2·CH3OH}n (1) (H2L = N,N′-bis(salicylidene)-1,4-butane-diamine), is afforded by the reaction of H2L with DyCl3·6H2O. X-ray crystallography analysis reveals that complex 1 features one-dimensional (1D) ionic double-chain structure. Magnetic studies suggest that the coordination polymer exhibits a typical SMM behavior under an external magnetic field.The flexible Salen-type dysprosium complex with 1D ionic coordination network represents the 4f SIMs.Display Omitted
Keywords: Salen-type; Dysprosium; Coordination polymer; 1D chain; Single molecule magnet;

Dinuclear iron(III) complexes, [(phenO)Fe(SO4)]2·2CH3OH (1) and [(bpmapO)Fe(NO3)]2(NO3)2·3CH3OH (2) have been prepared by the reaction of phenOH/bpmapOH and FeSO4·7H2O/Fe(NO3)3·9H2O in methanol, respectively (phenOH =  N-(2-pyridylmethyl)-N′-(2-hydroxyethyl)ethylenediamine, bpmapOH =  N-(bis(2-pyridylmethyl)amino)-2-methylpropan-2-ol). Both complexes are ethoxy-bridged dinuclear species and the iron(III) ions in 1 and 2 have distorted octahedral geometries. Both complexes show strong antiferromagnetic interactions through the bridged ethoxy groups within the dimeric units.Ethoxy-bridged dinuclear iron(III) complexes with tetradentate ligands have been prepared and structurally characterized. The iron(III) ions in the complexes have distorted octahedral geometries. Variable-temperature magnetic susceptibility measurements reveal that both complexes show strong antiferromagnetic interactions through the bridged ethoxy groups.Display Omitted
Keywords: Tetradentate ligand; Iron(III) complex; Crystal structure; Hydrogen bonding; Antiferromagnetic interaction;

A family of homochiral spin-crossover iron(II) imidazole Schiff-base complexes by Dong-Hong Ren; Xiao-Li Sun; Ling Gu; Dan Qiu; Zaijun Li; Zhi-Guo Gu (50-54).
Four novel homochiral mononuclear spin-crossover iron(II) complexes 14 have been successfully synthesized by subcomponent self-assembly of Fe(ClO4)2, 1-substituted imidazole-2-carboxaldehyde and optical phenylethylamine derivatives. X-ray crystallography revealed that the iron(II) center in 14 assumed an octahedral coordination environment with 6 N donor atoms from three unsymmetrical bidentate chiral Schiff-base ligands. [Fe(Ln)3]2 + components were chiral with either Λ or Δ configuration due to the screw coordination arrangement of the chiral ligands around Fe(II) center. Circular dichromism spectra confirmed the presence of non-racemic chiral metal centers in solution for 14. Magnetic measurements revealed that 14 displayed obviously spin-crossover behavior at 257, 375, 137 and 282 K, respectively. The different SCO behaviors of 14 may result from substitution effect, packing mode, and intermolecular interactions.Four novel homochiral mononuclear spin-crossover iron(II) complexes 14 have been successfully synthesized by subcomponent self-assembly. [Fe(Ln)3]2 + components in 14 were chiral with either Λ or Δ configuration due to the screw coordination arrangement of the chiral ligands around Fe(II) center. 14 displayed obviously spin-crossover behavior at 257, 375, 137 and 282 K, respectively.Display Omitted
Keywords: Homochiral; Iron(II); Spin-crossover; Schiff-base;

Heterometallic coordination framework by sodium carboxylate subunits and cobalt (III) centers obtained from a highly hydrogen bonding stabilized cobalt (II) monomeric complex by Jesús A. Arenzano; Jorge O. Virues; Raúl Colorado-Peralta; Pedro I. Ramirez-Montes; Rosa Santillán; Mario Sanchez; José María Rivera (55-60).
Coordination cobalt and nickel complexes (1) and (2) were obtained serendipitously by the reaction of M(NO3)2·6H2O (M = Co and Ni) and methyliminodiacetic acid (H2L) in a mixture of solvents. The X-ray diffraction showed the unusual structures with Z′ = 4 of (1) and (2), showing the four monomers highly stabilized by hydrogen bonding interactions which corresponds to the tris-(aqua)-(N-methyliminodiacetato)-cobalt (II) and nickel (II) respectively. The Wiberg Bond Indices (WBIs) were computed on (1) and (2) to evaluate the stability of the hydrogen bonding interactions and showed a good correlation with the experimental X-ray diffraction data. Finally, the complex [Co (L)2 Na]n (3) corresponds to the heterometallic coordination framework which was obtained by addition of a second equiv. of methyliminodiacetic acid (H2L) in basic sodium hydroxide media. The oxidation of the cobalt atom in (3) was confirmed by the experimental coordination bond distances observed by XRD, which are in the range from 1.882 to 1.957 Å.Coordination cobalt and nickel complexes (1) and (2) were obtained serendipitously by the reaction of M(NO3)2·6H2O (M = Co and Ni) and methyliminodiacetic acid (H2L) in a mixture of solvents. The X-ray diffraction showed the unusual structures with Z′ = 4 of (1) and (2), showing the four monomers highly stabilized by hydrogen bonding interactions which corresponds to the tris-(aqua)-(N-methyliminodiacetato)-cobalt (II) and nickel (II) respectively.Display Omitted
Keywords: Pseudosymmetry; Metal–organic frameworks; Hydrogen bonding; Theoretical calculations; Crystal engineering; Crystal packing;

New heteroleptic benzimidazole functionalized Ru-sensitizer showing the highest efficiency for dye-sensitized solar cells by T. Swetha; S. Niveditha; K. Bhanuprakash; Ashraful Islam; Liyuan Han; Idriss M. Bedja; Reza Fallahpour; Surya Prakash Singh (61-65).
We designed and synthesized a new ruthenium complex using terpyridine as an anchoring ligand and BOC (tert-butyloxycarbonyl) protected bidentate benzimidazole derivative as an ancillary ligand, coded as GS7. The complex was characterized using 1H NMR, FTIR, elemental analysis, UV–vis spectrophotometer, and cyclic voltammetry. We also tested photovoltaic performance of this complex for dye-sensitized solar cell (DSSCs). GS7 when used as a sensitizer for DSSCs with iodine triiodide electrolyte, showed a Jsc of 15.25 mA cm− 2, a Voc of 0.576 V, a FF of 0.691 and overall power conversion efficiency of (η) 6.07%.A new class of ruthenium complex with BOC-protected benzimidazole derivative as ancillary ligand was synthesized for DSSCs. GS7 based solar cell showed efficient panchromatic sensitization over the entire visible wavelength, showed a PCE of 6.07%.Display Omitted
Keywords: Benzimidazole; Photovoltaic performance; Dye sensitized solar cells (DSSCs); Iodine triiodide electrolyte; Power conversion efficiency;

The reaction of N,N-dimethylethylenediamino-N,N-bis(2,4-dimethylphenol) (H2L) (H2L) and MoCl5 gives a Mo(VI) complex [MoL(O)2] 1, which has been determined by X-ray crystallography. Electrochemical studies show that complex 1 can catalyze hydrogen evolution from acetic acid, trifluoroacetic acid and water with a turnover frequency (TOF) of 25.72 (acetic acid), 101.15 (trifluoroacetic acid) and 676 (buffer, pH 7.0) moles of hydrogen per mole of catalyst per hour, respectively.The reaction of N,N-dimethylethylenediamino-N,N-bis(2,4-dimethylphenol)(H2L) and MoCl5 gives a Mo(VI) complex [MoL(O)2] 1, a new molecular electrocatalyst, which has been determined by X-ray crystallography. 1 can catalyze hydrogen evolution from acetic acid, trifluoroacetic acid and water with a turnover frequency (TOF) of 25.72 (acetic acid), 101.15 (trifluoroacetic acid) and 676 (buffer, pH 7.0) moles of hydrogen per mole of catalyst per hour, respectively.Display Omitted
Keywords: Molybdenum(VI) complex; Molecular structure; Molecular electrocatalyst; Hydrogen evolution;

Highly porous titanium dioxide microspheres had been prepared via a template-assisted sol–gel process with cellulose nanofibril aerogel microsphere template. The modified porous titanium dioxide microspheres showed a typical super-hydrophobic property. The method reported in this study may be applied to fabricate other inorganic materials with desired porous structure.Highly porous TiO2 microspheres were synthesized by a sol–gel method using cellulose nanofibril microsphere aerogel as the template.Display Omitted
Keywords: Titanium dioxide microsphere; Porous structure; Template method; Sol–gel; Super-hydrophobic;

Heteroleptic chromium(III) tris(diimine) [Cr(N^N)2(N′^N′)]3 + complexes by Jonas Schönle; Edwin C. Constable; Catherine E. Housecroft; Markus Neuburger; Jennifer A. Zampese (75-77).
A series of heteroleptic tris(diimine) complexes of chromium(III) is reported and the crystal structures of {4[Cr(bpy)2(phen)][PF6]3}·11MeCN and 4[Cr(4,4′-Me2bpy)2(bpy)][PF6]3}·12MeCN·H2O are described. The combined effects of a 1:3 cation: anion ratio and lattice solvent molecules are discussed, in particular in the context of the influence on intercation embraces. The presence of the methyl substituents in {4[Cr(4,4′-Me2bpy)2(bpy)][PF6]3}·12MeCN·H2O results in Me–πbpy contacts becoming the dominant packing interactions and in the assembly of motifs distinct from those in {4[Cr(bpy)2(phen)][PF6]3}·11MeCN.The combined effects of a 1:3 cation:anion ratio and lattice solvent molecules in heteroleptic chromium(III) tris(diimine) complexes, particularly in the context of the influence on intercation embraces, have been investigated.Display Omitted
Keywords: Chromium; 2,2′-Bipyridine; 1,1-Phenanthroline; Heteroleptic complexes; Crystal structure; Chelates;

Kryptofix 5 forms complexes with a variety of metal cations. The coordination with the crown ether moiety affects only slightly the emission wavelength of the free Kryptofix 5 ligand (λmax  = 425 nm) in a buffer (pH = 9) solution, but the emission intensity of this blue fluorescence can increase strongly upon complex formation, probably owing to the rigidity of the complex. This applies e.g. to Ba2 +, Zn2 +, Cd2 +, Hg2 +, Ag+ and La3 +. A second group of metal ions such as Al3 +, Pb2 +, Sb3 +, Bi3 +, Te4 +, Gd3 + and Th4 + causes a large red shift of the fluorescence of free Kryptofix 5 to approximately λmax  = 500 nm. This green fluorescence resembles that of Kryptofix 5 in acidic solution. It is suggested, that the second group of metal ions is also coordinated to the pyridine nitrogen atoms of the quinoline substituents.The blue fluorescence of Kryptofix 5 is largely preserved, but intensified upon complexation of the metal ions Ba2 +, Zn2 +, Cd2 +, Hg2 +, Ag+, and La3 +, but it is replaced by a green fluorescence upon coordination of Al3 +, Pb2 +, Sb3 +,Bi3 +, Te4 +, Gd3 +and Th4 +.Display Omitted
Keywords: Fluorescence; Metal cations; Kryptofix 5; Cryptands;

The C-substituted charge-compensated dicarbollide [7-SMe2-7,8-C2B9H10]: Synthesis and room-temperature rearrangement of the iridium complex by Mikhail M. Vinogradov; Maria V. Zakharova; Sergey V. Timofeev; Dmitry A. Loginov; Igor B. Sivaev; Yulia V. Nelyubina; Zoya A. Starikova; Vladimir I. Bregadze; Alexander R. Kudinov (80-82).
The reaction of [7-SMe2-7,8-C2B9H10] with [(cod)IrCl]2 at room temperature affords iridacarborane 1-cod-8-SMe2-1,2,8-IrC2B9H10. The metal insertion is accompanied by polyhedral rearrangement of the carborane ligand with migration of the substituted carbon atom from the metal bonded pentagonal face. The electronic factors rather than steric ones play the main role in the ligand rearrangement. According to DFT calculations the final iridacarborane is more stable by 6–7 kcal mol− 1 than the transient pseudocloso-1-cod-2-SMe2-1,2,3-IrC2B9H10 complex. Structures of 7-SMe2-7,8-C2B9H11 and 2 were determined by X-ray diffraction.The reaction of [7-SMe2-7,8-C2B9H10] with [(cod)IrCl]2 is accompanied by room temperature cage rearrangement giving iridacarborane 1-cod-8-SMe2-1,2,8-IrC2B9H10.Display Omitted
Keywords: Boranes; Dicarbollide; Iridium; Metallacarboranes; Rearrangement;

Trans,trans,trans-[ReO2I2(PPh3)2], a rare rhenium(VI) complex — Synthesis and DFT study by J. Mukiza; T.I.A. Gerber; E. Hosten; A.S. Ogunlaja; F. Taherkhani; M. Amini; M. Nahali (83-86).
The heating of cis-[ReO2I(PPh3)2] at reflux in benzene in air led to the isolation of the rhenium(VI) complex [ReO2I2(PPh3)2] (1). The compound is centrosymmetric around the octahedrally coordinated rhenium center, and the Re=O bond length of 1.797(2) Å is longer than in typical trans-dioxorhenium(V) complexes. The asymmetric Re=O stretching frequency occurs at 744 cm− 1. Density functional theory has been used for the calculation of the vibrational spectrum density which confirms the experimental asymmetric Re=O stretching frequency. DFT calculation within the polarizable continuum model shows that complex 1 is more stable in CH2Cl2 than in the gas phase. EPR spectroscopy confirms a single d electron in 1. The crystal structure was determined by X-ray single crystal diffraction. In addition, infra-red, redox and electronic properties are also reported.The heating of cis-[ReO2I(PPh3)2] at reflux in benzene in air led to the isolation of the rhenium(VI) complex [ReO2I2(PPh3)2] (1). The compound is centrosymmetric around the octahedrally coordinated rhenium center, and the Re=O bond length of 1.797(2) Å is longer than in typical trans-dioxorhenium(V) complexes.Display Omitted
Keywords: Rhenium(VI); Dioxo; X-ray crystal structure; DFT; Solvent calculation; Vibrational spectrum density;

A new mononuclear Fe(III)–catecholate complex, which exhibits an incomplete spin transition without hysteresis, had been synthesized and structurally characterized. Analyzed from the structural characteristics, the tripodal ligand must play the important role in affecting the spin crossover (SCO) behavior. The larger steric strain effect and weak cooperativity existed in the crystal lattice are inclined to favor the incomplete transition.A new mononuclear Fe(III)–catecholate complex, which exhibits an incomplete spin transition without hysteresis, had been synthesized and structurally characterized. Analyzed from the structural characteristics, the tripodal ligand must play the important role in affecting the SCO behavior.Display Omitted
Keywords: Iron(III); Spin crossover; Catecholatol; Tripodal ligand;

An asymmetric naked-eye chemo-sensor for Cu2 + in aqueous solution by Hyun Yong Jo; Gyeong Jin Park; Kwon Hee Bok; Kyung-Min Park; Pahn-Shick Chang; Cheal Kim (90-94).
We have synthesized a new asymmetric chemo-sensor (E)-4-((2-((2-hydroxybenzylid-ene)amino)phenyl)amino)-3-nitro-2H-chromen-2-one (1) based on the combination of 2-hydroxybenzaldehyde and precursor 4-((2-aminophenyl)amino)-3-nitro-2H-chromen-2-one. Receptor 1 showed a selective color change from colorless to yellow in the presence of Cu2 + in aqueous solution. The detection limit (18 μM) of 1 for Cu2 + is lower than that (30 μM) recommended by WHO in drinking water, and sensor 1 could be recyclable simply through treatment with a proper reagent such as EDTA.A new asymmetric chemo-sensor 1 showed a selective color change from colorless to yellow in the presence of Cu2 +. The detection limit (18 μM) of 1 for Cu2 + is lower than that (30 μM) recommended by WHO in drinking water, and sensor 1 could be recyclable simply through treatment with a proper reagent such as EDTA.Display Omitted
Keywords: Copper; Colorimetric; Asymmetric; Reversible; Naked-eye;

Three Cu(II) coordination polymers with novel bi-triazole ligand: Synthesis, structure and EPR properties by Rui-Rui Cheng; Zhi-Lei Wu; Yin-Ling Hou; Jie Dong; Jian-Zhong Cui; Bin Zhao (95-98).
Three Cu(II) coordination polymers: [Cu(XL)(NO3)2]n (1), {[Cu(XL)(4,4′-bpy)(NO3)2]·CH3CN}n (1a) and {[Cu(XL)3](NO3)2·3.5H2O}n (2) have been synthesized mainly based on a novel bi-triazole ligand N,N′-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxdiimide bi(1,2,4-triazole) (XL) and characterized by X-ray crystallography, EPR spectra, elemental analyses, FT-IR spectra and PXRD patterns. Structure analyses reveal that compounds 1 and 1a exhibit 1D chains, and compound 2 features a 2D cationic framework. Additionally, the Cu(II) ions with various coordination environment in compounds 1, 1a and 2 exhibit different EPR properties.Three Cu(II) coordination polymers have been synthesized mainly based on a novel bi-triazole ligand. In these compounds, the Cu(II) ions with various coordination environments exhibit different EPR properties.Display Omitted
Keywords: Cu(II) coordination polymers; Bi-triazole ligand; EPR properties;

Dinuclear, tetrakis(acetato)-bridged lanthanide(III) complexes from the use of 2-acetylpyridine hydrazone by Nikolaos C. Anastasiadis; Ioannis Mylonas-Margaritis; Vassilis Psycharis; Catherine P. Raptopoulou; Dimitris A. Kalofolias; Constantinos J. Milios; Nikolaos Klouras; Spyros P. Perlepes (99-102).
The first employment of 2-acetylpyridine hydrazone in lanthanide(III) chemistry has led to dinuclear complexes with four bridging acetate groups of two different types and chelating 2-acetylpyridine hydrazone ligands.The use of the 2-acetylpyridine hydrazone/acetate/nitrate ligand “blend” in lanthanide(III) chemistry has resulted in dinuclear complexes containing two bridging and two bridging–chelating acetate groups, as well as chelating hydrazone and nitrato ligands.Display Omitted
Keywords: 2-Acetylpyridine hydrazone; Dinuclear lanthanide(III) complexes; Magnetic properties; Tetrakis(acetato)-bridged dilanthanide(III) complexes;

The preparation and catalytic property of palladium chloride catalyst supported on organic–inorganic hybrid nanorods by Kaiju Wei; Bo Zhang; Jia Ni; Junjun Geng; Jingwei Zhang; Dechen Xu; Yang Cui; Yangzhong Liu (103-105).
Two novel nano-catalysts with [Pd(dpa)Cl2] moiety have been synthesized by self-assembling organic–inorganic hybrid nanorods from 2,2′-dipyridylamine (dpa). The Pd2 + ions on the surface of the nanorods exhibit high activity for catalyzing Suzuki–Miyaura reactions.Display Omitted
Keywords: Palladium; Catalyst; Organic-inorganic Hybrid; Nanorods;

Under hydrothermal conditions, a new polynuclear Cu(II) complex, [Cu2(nip)(ina)(μ 3-OH)]2·H2O (1) (H2nip = 5-nitroisophthalic acid, Hina = isonicotinic acid) has been synthesized with mixed organic ligands. Single crystal X-ray analysis reveals that complex 1 displays a three-dimensional (3D) structure based on the tetranuclear Cu4 units. In the structure of 1, two pairs of symmetry-related Cu(II) ions are connected by six carboxyl and two μ 3-OH groups to generate the tetranuclear Cu4 units, which are connected by the mixed ligands into a 3D framework. Topology analysis reveals a (3,8)-connected tfz-d net for 1. Magnetic studies display antiferromagnetic behavior for 1. And thermogravimetric analysis of 1 has also been investigated.This paper reports a tetranuclear Cu(II) complex with a (3,8)-connected tfz-d net based on the tetranuclear Cu4 units, which displays antiferromagnetic interactions among the Cu(II) centers.Display Omitted
Keywords: Tetranuclear Cu(II) complex; Mixed ligands; tfz-d net; Magnetic property;

In this study a novel ligand with three carboxylic groups (H3L1) was synthesized. Its non-ion complex with GdL1 holding promise of magnetic resonance imaging (MRI) was synthesized, and the relaxivity of the complex determined. The relaxivity of GdL1 (R 1  = 4.5 Mmol− 1·s− 1) was larger than that of Gd(DTPA)2 −(R 1  = 3.9 Mmol− 1·s− 1). The results showed that the non-ion complex is a prospective MRI contrast agent.
Keywords: Magnetic resonance imaging; Macrocycle; Gadolinium; Relaxivity; Contrast agent;

Oxidative dehydrogenation of 5-(pyridine-2-yl-methyl)-2-thioxo-4-imidazolidinones in complexation reaction with copper(II) chloride by Alexander G. Majouga; Elena K. Beloglazkina; Anna V. Yudina; Andrei V. Mironov; Nikolay V. Zyk (114-117).
The treatment of 5-(pyridine-2-yl-methyl)-2-thioxo-4-imidazolidinones with copper(II) chloride dihydrate led to the formation of a dinuclear copper complex L2Cu2Cl where L is a dehydrogenated initial organic ligand. X-ray diffraction analysis indicated that the starting 3,5-dihydro-4H-imidazole-4-ones undergo oxidation in the course of the reaction with the formation of an exocyclic double bond at C5 position.The treatment of 5-(pyridine-2-yl-methyl)-2-thioxo-4-imidazolidinones with copper(II) chloride dihydrate led to the formation of a dinuclear copper complex L2Cu2Cl where L is a dehydrogenated initial organic ligand.Display Omitted
Keywords: Copper complexes; Ligand oxidation; Dehydration;

The N-(2-carboxyphenyl)salicylideneimine ligand in 4f-metal chemistry: A unique neodymium(III) chain containing the singly deprotonated, zwitterionic form of the ligand by Nikolaos C. Anastasiadis; Nikolia Lalioti; Aris Terzis; Vassilis Psycharis; Catherine P. Raptopoulou; Spyros P. Perlepes (118-121).
The reactions of N-(2-carboxyphenyl)salicylideneimine and hydrated praseodymium(III) or neodymium(III) chlorides give 1D complexes with interesting structural and spectroscopic features; the chains possess the singly deprotonated ligand which is in its zwitterionic form.The synthetic investigation of the neodymium(III) chloride/N-(2-carboxyphenyl)salicylideneimine system has provided access to an interesting 1D coordination polymer comprising the singly deprotonated, zwitterionic form of the ligand, which forms an unusual 10-membered chelating ring and bridges two metal ions.Display Omitted
Keywords: Chain compounds; N-(2-carboxyphenyl)salicylideneimine; Neodymium(III) complexes; Praseodymium(III) complexes; Zwitterionic ligands;

Hydrothermal syntheses and crystal structures of four novel lanthanide(III) complexes based on two mixed N,O-donor ligands by Xing-Jing Zhang; Wei-Kang Li; Wen-Tong Zhang; Guang-Bo Che; Xiu-Ying Li; Yu Qiao; Cheng-Cheng Zhao (122-125).
Four novel polymeric lanthanide(III) complexes [Pr(NCP)(2,5-pydc)]n·1.5nH2O (1), [La(NCP)(2,5-pydc)]n (2), [Nd(NCP)(2,5-pydc)]n (3) and [Sm(NCP)(2,5-pydc)]n (4) (HNCP = 2-(4-carboxyphenyl)imidazo(4,5-f)(1,10)phenanthroline, 2,5-H2pydc = pyridine-2,5-dicarboxylic acid) have been hydrothermally synthesized and characterized via elemental analysis and single crystal X-ray diffraction. Structural analyses revealed that all of these four complexes possess similar two-dimensional sheet structures, which are further linked by the hydrogen bonds to furnish three-dimensional supramolecular structures. Meanwhile, the thermogravimetric analysis and photoluminescent property of complexes 14 have also been investigated.A series of lanthanide (III) coordination polymers with intriguing structures based on 2-(4-carboxyphenyl)imidazo(4,5-f)(1,10)phenanthroline and pyridine-2,5-dicarboxylic acid ligands have been hydrothermally synthesized. The thermal stabilities and photoluminescence properties of these complexes have been investigated.Display Omitted
Keywords: Lanthanide(III) complex; 2-(4-Carboxyphenyl)imidazo(4,5-f)(1,10)phenanthroline; Pyridine-2,5-dicarboxylic acid; Crystal structure;