Inorganic Chemistry Communications (v.76, #C)

Contents List (iii-xi).

Six-coordinate oxo-vanadium(V) dimer complex with methoxy bridging: Synthesis, crystal structure, biological activity and molecular docking by Farideh Heidari; S. Jamil A. Fatemi; S. Yousef Ebrahimipour; Hadi Ebrahimnejad; Jesús Castro; Michal Dušek; Václav Eigner (1-4).
A diketone-based tridentate Schiff base, 3-[(2-hydroxyphenyl)amino]-1,3-diphenylprop-2-en-1-one (H2L), and its oxo-vanadium(V) dimer complex, [VO(L)(OMe)]2, were synthesized and characterized using spectroscopic and physicochemical techniques. Single crystal X-ray diffraction indicated that the Schiff base ligand in its deprotonated form was found to bind to the V(V) ion through the azomethine nitrogen, amine and phenolic oxygens in a distorted octahedral geometry. The other positions around the V(V) center were occupied by an oxido group and two oxygens from methoxido ligands. Antimicrobial studies showed that the synthesized complex indicated significant antimicrobial activities against Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 33591 and 29213) bacteria while no antibacterial activity was observed for the ligand alone. The potential of [VO(L)(OMe)]2 as an antimicrobial agent, was additionally investigated using molecular docking of the complex with GlcN-6-P synthase.Display Omitted
Keywords: Oxo-vanadium(V); Schiff base complex; Antimicrobial activity; X-ray crystal structure;

Riboflavin reacts with Pt(C6H5CN)2Cl2 in acetic acid to yield insoluble [Pt(riboflavin)4]Cl2. This brown compound shows a bright yellow-orange photoluminescence with λmax  = 635 nm. This emission is suggested to originate from the lowest-energy IL (riboflavin) triplet. This assignment is based on the comparison to the photoluminescence of solid riboflavin which exhibits a fluorescence as well as a phosphorescence, again under ambient conditions.Display Omitted
Keywords: Platinum; Riboflavin; Photoluminescence; Phosphorescence;

[C6H11S(CH2)3C4H9N2C6H5Cl (L1Cl)] has been synthesized by reaction of cyclohexyl thiol with 1-(chlorophenyl)-4-(3-chloropropyl) piperazine hydrochloride ( P 1 ) under dry nitrogen atmosphere. The L 1 Cl on reaction with Cd(NO3)2 forms a compound [L 1 NO 3 ] having NH―O hydrogen bonding. The single crystal structure of the compound L1NO3 is solved. The characteristic feature of these reactions is the retention of the piperazinium character from starting material ( P 1 ) to ligand formation (L 1 Cl) as well as in the formation of anion exchange product (L 1 NO 3 ). L1Cl and L1NO3 are characterized on the basis of physico-chemical and spectral (ESI Mass, FT-IR, 1H, 13C and DEPT 135° 13C {1H} NMR) studies. The proton and carbon-13 NMR spectra of L 1 Cl and L 1 NO 3 are characteristic. L 1 NO 3 crystallizes in orthorhombic system with Pbca space group. Both piperazine and cyclohexane rings adopt the chair conformation with N1, N2 and C14, C17 out of plane. Geometry around quaternary nitrogen atom is distorted tetrahedral as revealed by the bond angles.Display Omitted
Keywords: Anion exchange; Orthorhombic; Piperazine; Space group;

NIR luminescence comparison of Zn-Nd Schiff-base complex doped or single-nodal grafted into PMMA by Guorui Fu; Peiyang Su; Xingqiang Lü; Wai-Kwok Wong (12-14).
Through doping or grafting of a new ZnNd Schiff-base complex monomer [Zn(L)(4-vinyl-Py)Nd(NO3)3] (2; H2L =  N,N′-bis(3-methoxy-salicylidene)phenylene-1,2-diamine; 4-vinyl-Py = 4-vinyl-pyridine) into PMMA (poly(methyl methacrylate)), two kinds of hybrid materials 2@PMMA and Poly(2-co-MMA) with significantly improved physical properties including good Nd3 +-centered near-infrared (NIR) luminescence were obtained. Especially the single-nodal ZnNd-grafted Poly(2-co-MMA) soluble in organic solvents exhibits the high sensitization efficiency (η sens  =  Φ Nd L/Φ Nd Nd  = 81%) even at a high feed molar ratio up to 1:50.Single-nodal ZnNd-Schiff-base-grafted hybrid materials Poly(2-co-MMA) endow the good solubility and the higher sensitization efficiency (η sens  =  Φ Nd L/Φ Nd Nd  = 81%) even at a high feed molar ratio up to 1:50 than that of the doping hybrid materials 2@PMMA.Display Omitted
Keywords: Vinyl-functionalized ZnNd Schiff-base complex monomer; PMMA-supported hybrid material; NIR luminescence;

[Zn(H2O)4][B6O10]: An open-framework borate with acentric structure by Rui Pan; Bai-Feng Yang; Guo-Ming Wang; Guo-Yu Yang (15-17).
An open-framework borate [Zn(H2O)4][B6O10] with acentric structure, has been successfully obtained for the first time under solvothermal conditions. It has been characterized by powder and single crystal X-ray diffraction, IR spectroscopy, diffuse-reflectance spectroscopy and thermogravimetric (TG) analyses, respectively. It crystallizes in the orthorhombic system, space group Pna21, a = 11.3140(6) Å, b = 11.8995(7) Å, c = 8.6140(5) Å and Z = 4. In the structure, the alternative connections between [B3O7] units give rise to an unprecedented 3D borate framework with 11- and 10-MR channels, in which the [Zn(H2O)4]2+ complexes are located. It has a cut-off edge below 200 nm and exhibits second harmonic generation (SHG) efficiency approximately 0.4 times that of KH2PO4 (KDP).A new 3D open-framework borate [Zn(H2O)4][B6O10] (1) with acentric structure has been solvothermally prepared and structurally characterized. The alternative connections between [B3O7] units give rise to an 3D borate framework with 11- and 10-MR channels. Compound 1 exhibits SHG signals approximately 0.4 times that of KH2PO4 (KDP).Display Omitted
Keywords: Open-framework; Oxoboron cluster; Solvothermal condition; Nonlinear optical; Crystal structure;

A novel neodymium-organic framework (Nd-MOF) based on Nd(III) dinuclear nodes, with formula {[Nd2(NH2-BDC)3(DMF)4]}n (1) (NH2-BDC = 2-aminoterephthalic acid), was synthesized under solvothermal conditions, characterized by fourier transform infrared spectrum measurements, thermogravimetric analysis, powder X-ray diffraction and single crystal X-ray diffraction. The structure of 1 is octahedral networks constructed by infinite connection of the cube units, in which each cube unit is formed by using the neodymium dinuclear nodes linked via the NH2-BDC ligands as the vertexes, then the eight vertexes are joined each other by the NH2-BDC ligands again to give a cube unit. Photoluminescence measurement indicates that 1 exhibits excellent near infrared luminescence. In addition, 1 displays rapid and selective sensing of Cu2 +, which represents the first near infrared fluorescent probe of MOFs used for detection.A novel Nd-MOF {[Nd2(NH2-BDC)3(DMF)4]}n (1) based on Nd(III) dinuclear nodes is synthesized and structurally characterized. 1 displays the octahedral networks linked by infinite connection of the cube units, in each cube unit the dinuclear nodes are used as the vertexes. Near infrared luminescent measurements indicate that 1 can detect Cu2 + with high sensitivity and selectivity, it represents the first near infrared fluorescent probe of MOFs used in detection.Display Omitted
Keywords: Neodymium-organic framework; 2-Aminoterephthalic acid; Crystal structure; Near infrared fluorescent probe; Detection; Copper cation;

A novel 1-D coordination polymer constructed from disilver-1,3,4-oxadiazole nodes and perchlorato bridges by Catalin Anghel; Mihaela Matache; Codruta C. Paraschivescu; Augustin M. Madalan; Marius Andruh (22-25).
The reaction of silver perchlorate with 2-phenyl-5-(p-tolyl)-1,3,4-oxadiazole (L) affords a 1-D coordination polymer, [Ag3 L 4(ClO4)3] (1). Two silver ions are bridged by two L ligands, through the nitrogen atoms of the oxadiazole ring, resulting in binuclear units. The coordination polymer is constructed from binuclear nodes, {Ag2 L 2}, connected by perchlorato bridges. The investigation of the optical properties of compound 1 indicates a slight change in the emission profile compared to the organic ligand, showing blue luminescence upon excitation at λ = 300 nm.Display Omitted
Keywords: Silver coordination polymer; 2,5-Disubstituted-1,3,4-oxadiazole; Perchlorato bridges; Blue luminescence;

An aluminoborate directed by [Zn(H2O)4]2 + complex: Synthesis, structure and properties by Rui Pan; Bai-Bai Yang; Guo-Ming Wang; Guo-Yu Yang (26-29).
A novel 3D aluminoborate with [Zn(H2O)4]2+ cationic complexes as structure-directing agents (SDAs), namely, [Zn(H2O)4][Al(B5O10)]·0.5(H2O) (1), has been solvothermally prepared and characterized by IR spectroscopy, UV–vis reflection spectroscopy, thermogravimetric (TG) analyses, powder and single crystal X-ray diffraction, respectively. The alternative linkage of AlO4 tetrahedra and B5O10 units produces an open-framework aluminoborate with helical 6- and 8-membered ring (MR) channels, as well as large odd 11-MR channels. The [Zn(H2O)4]2+ templates, generated in situ from solvothermal conditions, are orderly located in the center of the 11-MR channels. The second-harmonic generation (SHG) measurement indicates that 1 exhibits about 0.5 times that of KDP standard (K2HPO4).A novel 3D aluminoborate [Zn(H2O)4][Al(B5O10)]·(H2O)0.5 (1) with [Zn(H2O)4]2 + template has been solvothermally synthesized. It possesses a 3D framework built from AlO4 tetrahedra and B5O10 units. Intersecting helical channels and large odd 11-MR channels have been observed in the framework.Display Omitted
Keywords: Aluminoborate; Solvothermal synthesis; Crystal structure; Nonlinear optical;

Through the ring-opening metathesis polymerization (ROMP) of norbornene (NBE) with each of the obtained allyl-containing complex monomers {[Ln3(L)4Cl4(MeOH)2]·Cl} (Ln = La, 1; Nd, 2; Yb, 3; Er, 4 or Gd, 5; HL  = 4-allyl-2-(1H-benzo[d]imidazol-2-yl)-6-methoxyphenol), a series of metallopolymers Poly({[Ln3(L)4Cl4(MeOH)2]·Cl}-co-NBE) were obtained, respectively. Especially for Poly(NBE-co-2) and Poly(NBE-co-3), covalently-bonded grafting endows significantly improved physical properties including efficient NIR luminescence (Φ Nd L  = 0.58% and Φ Yb L  = 0.88%) in solid state.Within series of new PNBE-supported metallopolymers Poly({[Ln3(L)4Cl4(MeOH)2]·Cl}-co-NBE) (Ln = La, Nd, Yb, Er or Gd), Nd3-containing Poly(2-co-NBE) and Yb3-containing Poly(3-co-NBE), endow significantly improved physical properties including efficient solid state NIR luminescence (Φ Nd L  = 0.58% and Φ Yb L  = 0.88%).Display Omitted
Keywords: Allyl-containing Ln3-benzimidazole-arrayed complex monomer; PNBE-supported metallopolymer; ROMP; NIR luminescence;

The first example of mechanochemical synthesis of organometallic pincer complexes by Diana V. Aleksanyan; Svetlana G. Churusova; Rinat R. Aysin; Zinaida S. Klemenkova; Yulia V. Nelyubina; Vladimir A. Kozlov (33-35).
The synthesis of an organometallic PdII pincer complex is realized for the first time via C―H bond activation of the bis(thiocarbamate) ligand with PdCl2(NCPh)2 under mechanochemical conditions either by grinding of the reactants in a mortar or in a vibration ball mill at gram scale.Display Omitted
Keywords: Cyclometalation; Pincer complexes; Palladium; Solid-state synthesis;

N,C,N-intramolecularly coordinated antimony(III) and bismuth(III) oxides (ArMO)2 [where Ar = [2,6-(Me2NCH2)2C6H3], M = Sb (1) or Bi (2)] reacted with 1,1′-ferrocenedicarboxylic acid fc(COOH)2 (fc = ferrocene-1,1′-diyl) under formation of corresponding carboxylates fc(COO)2SbAr (4) and [fc(COO)2BiAr]2 (5). Similarly, the treatment of fc(COOH)2 with tin(IV) carbonate ArSnPhCO3 (3) led to the carboxylate fc(COO)2Sn(Ph)Ar (6). All compounds were characterized by the help of multinuclear NMR, Raman, IR and UV–Vis spectroscopy and in the case of 4 and 5 using single-crystal X-ray diffraction analysis.Rare examples of antimony(III) and bismuth(III) ferrocene carboxylates, derivatives of 1,1′-ferrocenedicarboxylic, acid were prepared and characterized.Display Omitted
Keywords: Antimony; Bismuth; Tin; Chelating ligands; Carboxylates; Ferrocene;

Nitrosyl cis-dichlorodiammine ruthenium complex with bridging H3O2 ligand by Vasily Vorobyev; Vyacheslav A. Emelyanov; Igor A. Valuev; Iraida A. Baidina (40-43).
The ruthenium complex with bridging H3O2 ligand was obtained and the crystal structure was determined. The compound cis-[{RuNO(NH3)2Cl2}22-H3O2)]Cl crystallizes in the monoclinic space group P21/n with cell parameters a  = 15.0651(5), b  = 6.3624(2), c  = 15.3813(6) Å, β  = 94.9690(10)°, Z = 4 and R  = 0.0185. The hydroxide hydrate anion is coordinated to the ruthenium atoms of the identical cis-{RuNO(NH3)2Cl2} fragments. The protonation of the starting cis-[RuNO(NH3)2(NO2)2OH] complex leads to the required coordinated aqua/hydroxide ratio if the specific amount of hydrochloric acid is used. The DFT calculations confirm the formation of the dimer structure in the gas phase. However, the presence of water molecules dramatically reduces the dimerization efficiency.Display Omitted
Keywords: Ruthenium; Nitrosyl; Ammine complex; Chloro complex; Aqua-hydroxo ligand;

Photoinduced chromism of a Zinc–Iron cyanide at room temperature by Xiang-Ying Lv; Lin-Hui Zhang; Xiao-Pin Li; Xin Zhang (44-47).
A room temperature (RT) chromism induced by illumination of ~ 250–450 nm light was observed for the first time in a Prussian blue analog, K0.26Zn2.87[Fe(CN)6]2·7.2H2O. The photoinduced chromism is caused by the charge transfer from CN to Fe3 + as manifested by IR and XPS measurements. Such an obvious chromic property controlled by certain optical stimuli at RT may have potential applications in optical devices.A room temperature photoinduced chromism of a Prussian blue analog, K0.26Zn2.87[Fe(CN)6]2·7.2H2O, was observed for the first time by the illumination of ~ 250–450 nm light. The mechanism of this chromism is caused by the charge transfer from CN to Fe3 + as manifested by IR and XPS measurements.Display Omitted
Keywords: Photoinduced chromism; Zinc-iron cyanide; Prussian blue analog; Charge transfer;

Two phenoxo-O bridged Dy2 complexes based on 8-hydroxyquinolin derivatives with different magnetic relaxation features by Wen-Min Wang; Song Wang; Zhi-Lei Wu; Yun-Gen Ran; Yue-Hong Ren; Cai-Feng Zhang; Ming Fang (48-51).
Two new dinuclear dysprosium compounds, namely, [Dy2(L1)2(hfac)6]·C7H16 (1) and [Dy2(L2)2(hfac)6]·C7H16 (2) (HL1 = 5-(2-thenylidene)-8-hydroxylquinoline; HL2 = 5-(4-methoxylbenzylidene)-8-hydroxylquinoline; hfac = hexafluoroacetylacetonate) have been successfully obtained via applying two different ligands, and further characterized by crystallography. Structural analysis shows that both of 1 and 2 possess a four-membered [Dy2O2] core with similar coordination pockets. The center Dy(III) ions in 1 and 2 are all completed by eight coordination environments with O8 set. Interestingly, the different features of ligand HL1 and HL2 result in their different magnetic relaxation behaviors with the energy barrier of 6.81 K for 1 and 0.72 K for 2. 1 and 2 are both phenoxo-O bridged binuclear complexes. Magnetic measurements indicated that they exhibit different magnetic relaxation behaviors with the energy barrier (ΔE/k B) 6.81 for 1 and 0.72 for 2.Display Omitted
Keywords: 8-Hydroxyquinoline; Dinuclear dysprosium; Magnetic relaxation behaviors;

A cobalt complex of a pentadentate aminopyridine ligand as an efficient catalyst for photocatalytic hydrogen generation by Xiao-Wei Song; Yan Meng; Chuan-Lei Zhang; Cheng-Bing Ma; Chang-Neng Chen (52-54).
A linear pentadentate aminopyridine ligand 2,6-bis[(methyl(pyrid-2-ylmethyl)amino)-N-methyl]pyridine (PyMepam) has been prepared and characterized. This ligand readily coordinates with Co(II) or Zn(II) ions, and the resulting complexes of general formula [M(PyMepam)](BF4)2 (M = Co (1) and M = Zn (2)) have been thoroughly characterized and investigated for electro- and photocatalytic water reduction in acetonitrile. Electrochemical studies reveal that the complex 1 is active for electrocatalytic water reduction in acetonitrile. Under visible-light irradiation (λ > 400 nm), the complex 1 displays hydrogen evolution activity when in presence of [Ir(ppy)2(bpy)]PF6 as photosensitizer and triethylamine (TEA) as electron donor, whereas 2 shows negligible catalytic activity under the same conditions. Highest turnover numbers (TONs) of 290 for H2 evolution are achieved from an optimized system containing 1 (0.1 mM), [Ir(ppy)2(bpy)](PF6) (0.5 mM), and 10 vol% TEA in CH3CN-H2O (1/1, v/v) mixed solvents at pH 10.A cobalt complex of a linear pentadentate aminopyridine ligand was active for photocatalytic hydrogen production with a highest TON of 290.Display Omitted
Keywords: Cobalt; Aminopyridine ligand; Hydrogen evolution; Photocatalysis;

Controllable antiferromagnetic to ferromagnetic coupling in polynuclear Fe(III)–Co(II) heterobimetallic complexes by Jun-Li Wang; Hai-Lang Zhu; Liang Zhao; Ling-Xiang Ren; Chun-Ying Duan; Tao Liu (55-58).
A tetranuclear cluster {[(Tp)Fe(CN)3]Co(pp)H2O}2·[(Tp)Fe(CN)3]2  ⋅ 6H2O (1; Tp = hydrotris(pyrazoly)borate, pp = 2,6-bis(N-pyrazolyl)pyridine) and a hexanuclear cluster {[(pzTp)Fe(CN)3]2Co(pp)}2·2H2O (2; pzTp = tetrakis(pyrazoly)borate) have been synthesized via rational assembly of the same (ppCoII)2 + unit and different tricyanometalate building blocks with varying proportions of sterically hindered groups. Magnetic measurements reveal that 1 exhibits the dominant antiferromagnetic interactions between Fe(III) and Co(II) ions, while 2 exhibits the dominant ferromagnetic interactions.From a tetranuclear Fe2Co2 cluster to a hexanuclear Fe4Co2 cluster was synthesized based on different cyanometalate building blocks with varying proportions of sterically hindered groups. The corresponding magnetic properties change from antiferromagnetic interaction to ferromagnetic interaction.Display Omitted
Keywords: Antiferromagnetic; Ferromagnetic; Polynuclear; Heterobimetallic system;

Two novel Ln-radical chains [Ln(hfac)3NIT-3Py-5Im]n (LnIII  = Gd 1, Dy 2; hfac = hexafluoroacetylacetonate; NIT-3Py-5Im = 2-(5-(1-imidazole)-3-pyridyl)-4,4,5,5- tetramethylimidazoline-1-oxyl-3-oxide) have been achieved. In two complexes, the functionalized radical ligand NIT-3Py-5Im acts as bridge ligand to link two Ln(III) ions through the NO group and the imidazole ring, leading to rare 1D lanthanide-radical chains. Magnetic studies show that antiferromagnetic interactions dominate in the system owing to the short contacts of NO groups between the chains.Two novel 1D chain Ln-rad complexes were obtained and antiferromagnetic interactions dominated in these complexes due to the short contacts of inter-chain NO groups.Display Omitted
Keywords: Functionalized nitronyl nitroxides; Lanthanide; One-dimensional chain; Magnetic properties;

Structural differences of half-sandwich complexes of scandium and yttrium containing bulky substituents by Adéla Fridrichová; Aleš Růžička; Martin Lamač; Michal Horáček (62-66).
Scandium and yttrium half-sandwich chloride complexes (η 5-C5Me4R)ScCl2(THF)2 R = CH2Ph (3) or SiMe2CH2CH2Ph (5) and (η 5-C5Me4R)YCl2(THF)2 R = CH2Ph (4) or SiMe2CH2CH2Ph (6) were prepared by metathetic reactions of the corresponding substituted lithium or potassium cyclopentadienides with scandium or yttrium trichloride. A mutual comparison of the determined solid state structures of 4 and 5 revealed the tetranuclear character in the case of scandium complex containing C5Me4SiMe2CH2CH2Ph ligand, while a formation of the trinuclear ate-complex 4 incorporating lithium was observed for the combination of yttrium and the benzyl substituted tetramethyl cyclopentadienyl. Moreover, the steric effect of addition of another differently substituted cyclopentadienyl ring into the molecule was evaluated.Scandium and yttrium half-sandwich chloride complexes (η 5-C5Me4R)ScCl2(THF)2 R = CH2Ph (3), R = SiMe2CH2CH2Ph (5) and (η 5-C5Me4R)YCl2(THF)2 R = CH2Ph (4), R = SiMe2CH2CH2Ph (6) were prepared and the influence of various substitution of the cyclopentadienyl ligand on solid state structures of the resulting complexes was investigated.Display Omitted
Keywords: Scandium; Yttrium; Half-sandwich; Metallocene; Steric effect;

1,4-Diazabicyclo [2,2,2]octane N,N′-dioxide di(perchlorate), C6H14N2O2 2 +·2ClO4 , was synthesized and separated as colorless block crystals. Differential scanning calorimetry detected that this compound underwent a reversible phase transition at ca. 216 K with a hysteresis of 5.5 K width, which was also confirmed by dielectric measurements. Single crystal X-ray diffraction data suggested that there was a transition from a room temperature phase with the space group of P21/c (a  = 6.815(7) Å, b  = 12.644(13) Å, c  = 8.676(9) Å, β  = 101.466(15)°, V  = 732.7(13) Å3, Z  = 4) to a low temperature one with a space group of P21 (a  = 9.892(8) Å, b  = 12.559(10) Å, c  = 17.401(13) Å, β  = 92.065(8)°, V  = 2160(3) Å3, Z  = 2). Crystallographic analysis showed that it belonged to chiral space group P21 with ferroelectric behaviors, and a typical ferroelectric feature of electric hysteresis loop was obtained in the low temperature phase. The disorder-order transformation of H2-Dabcodo2 + cation and ClO4 anion as well as the change of hydrogen bonds may drive the phase transition.1,4-Diazabicyclo [2,2,2]octane N,N′-dioxide di(perchlorate) with ferroelectric behavior at low temperature phase was synthesized and separated as colorless block crystals. Crystallographic analysis showed that it belonged to chiral space group P21 with ferroelectric behaviors, and a typical ferroelectric feature of electric hysteresis loop was obtained in the low temperature phase.Display Omitted
Keywords: Phase transition; Ferroelectric; Variable-temperature X-ray; Dielectric constant;

Influence of Mn-doping on the photocatalytic and solar cell efficiency of CuO nanowires by Muzaffar Iqbal; Akbar Ali Thebo; Aamir Hassan Shah; Azhar Iqbal; Khalid Hussain Thebo; Shahnawaz Phulpoto; Muhammad Ali Mohsin (71-76).
Pristine copper oxide (CuO) and manganese (Mn) doped CuO nanostructures with different ratios were synthesized via wet chemical method. As-prepared materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-rays (EDX), UV–Visible and emission spectroscopy. Further, the doped nanowires were employed in the hybrid solar cells in combination with P3HT and gave better current densities than their corresponding undoped counterparts. The photoactivity of synthesized materials was evaluated by the photocatalytic oxidation of Rhodamine B (RhB). The results showed that the 2% Mn doped CuO photocatalyst is highly photoactive than other corresponding undoped and doped CuO nanowires. The increase in solar cell efficiency and photocatalytic activity of the doped CuO nanowires is solely due to the improvement in the charge separation efficiency in the 2% Mn doped CuO nanowires.Environment friendly and low cost method has been used to synthesize CuO nanowires with different doping concentrations of Mn. The photo activity of doped nanowires was evaluated by the photocatalytic oxidation of Rhodamine B (RhB). The results showed that the 2% Mn doped CuO photocatalyst is much highly photoactive than non-doped or highly doped CuO. Further, the doped nanowires were employed in the hybrid solar cells in combination with P3HT and gave better current densities than their corresponding undoped counterparts.Display Omitted
Keywords: CuO; Wet chemical method; Nanowire; Rhodamine B; Photocatalyst;

By employing a triphenylamine moiety functionalized luminescent ligand, a new water-stable lanthanum-based coordination polymer {[La(HNTB)2(HPY)](H2O)6}n (1, H3NTB = 4.4′,4″-nitrilotrisbenzoic acid, PY = pyridine) has been successfully synthesized, structurally identified and further used as a fluorescent probe for selective detection of Fe3 + ion and nitrobenzene vapor. Compound 1 is composed of a binuclear La unit that connected by the partly deprotonated HNTB2 − ligand to afford a novel (3,12)-connected framework whose topology has not been reported so far. Notably, compound 1 exhibits robust architecture in water and shows strong blue emission under UV excitation, based on which it could behave as a fluorescent probe for selective detection of Fe3 + ion with good stability and recyclability. Additionally, 1 also shows a fast response to trace amount of nitrobenzene vapor via a fluorescence quenching.A water-stable La-based coordination polymer has been prepared by employing a triphenylamine moiety functionalized luminescent ligand. This compound not only possesses a novel (3,12)-connected framework structure, but also could behave as a fluorescent probe for selective detection of Fe3 + ion with good stability and recyclability in water. Additionally, this compound also shows a fast response to trace amount of nitrobenzene vapor via a fluorescence quenching.Display Omitted
Keywords: La-based coordination polymer; (3,12)-Connected topology; Water-stable; Fluorescent probe;

A ligand based on 3-((quinoline-7-yl) methyeleneamino) phenazine-2-ol) (HAPQA) has been designed and synthesized for the selective detection of cyanide ions. The ligand HAPQA exhibits excited-state intramolecular proton transfer (ESIPT) with a long wavelength emission fluorescent (575 nm) which gradually quenches with the addition of cyanide ions. The photophysical properties of the probe as well as its selectivity towards CN ions are explored using UV–visible, emission spectroscopy and time-resolved fluorescence spectroscopic studies. The ligand exhibits strong H-bonding-mediated inhibition of 2-way excited-state intramolecular proton transfer (ESIPT) in HAPQA selectively with cyanide ions over all other ions. The deep orange colour fluorescence of the ligand in acetonirile turns into bright green coloured solution in presence of cyanide ions with a detection limit of 0.60 μM. DFT calculations has been done to study the ground and excited state energy optimized structure and proposed mechanism which is in harmony with the experimental findings and the ESIPT process observed in ligand HAPQA. Thus, the receptor can be used as a Colorimetric and fluorescent sensor for the determination of CN ion.A ligand based on 3-((quinoline-7-yl) methyeleneamino) phenazine-2-ol) (HAPQA) has been synthesized and used for the selective detection of cyanide ions. The ligand has been designed in such a way so that the excited state intramolecular proton transfer (ESIPT) of the HAPQA moiety gets blocked. The deep orange (λem = 575 nm) fluorescence of HAPQA in acetonirile turns into bright green fluorescence (λem = 505 nm) in presence of the cyanide (detection limit = 0.60 μM).Display Omitted
Keywords: CN ions; ESIPT; H-bonding-mediated inhibition; DFT;

Solid-state phase transition induced by ordering of flexible chain alkylamine in N-ethyl-n-butylammonium 3, 5-dinitrobenzoate monohydrate by Sasa Wang; Bingqing Zhao; Ting Zhang; Chengmin Ji; Muhammad Adnan Asghar; Lina Li; Zhihua Sun; Zhenyue Wu; Junhua Luo (87-90).
A new molecule-based compound, N-ethyl-n-butylammonium 3, 5-dinitrobenzoate monohydrate, which undergoes a reversible solid-state phase transition at 197 K (T c ), has been successfully constructed based on long-chain alkylamine. Specific heat capacity and differential scanning calorimetry (DSC) measurements confirm that it is first-order phase transition with a 5 K thermal hysteresis between heating and cooling scans. Dielectric constants exhibit distinct anomalies around T c accompanied with step-like responses between low and high dielectric states, which further confirm the phase transition. Variable-temperature single-crystal X-ray diffraction analyses illustrate that the phase transition was elucidated from ordering of the flexible N-ethyl-n-butylammonium cations coupled with reorientational motion of the alkylamine chain.Flexible long-chain alkylamine enables to regulate the construction of phase transition by the reorientational motion of the moiety.Display Omitted
Keywords: Phase transition; First-order; Dielectric anomaly; Order-disorder;

A metal-organic framework with unusual nanocages: Drug delivery by Zhidong Luo; Rui Wang; Chuying Gu; Fumei Li; Yaoyao Han; Baohong Li; Jianqiang Liu (91-94).
An unusual nanocage-based framework of [Zn2(L)(H2O)1.5]·5H2O (1) was used as a drug carrier of 5-fluorouracil (5-FU) for drug delivery. The incorporation of drug 5-FU into the 1 was around 48.6 wt% per gram of dehydrated 1. 5-FU is released in a highly controlled and progressive manner with 98% of the drug release after 101 h at acidic condition and with 62% after 72 h at PBS. 1 did not exhibit any significant cytotoxicity using the vitro cytotoxicity assays. The result from this study suggested a new approach for MOFs to be used as potential drug delivery.A new MOF was used as a drug vehicle of 5-fluorouracil (5-FU) for drug delivery. The cargo release behavior and material degradation profile were also investigated under different pH.Display Omitted
Keywords: Nanocage; Drug delivery; Cytotoxicity assay;

To seek novel dysprosium based single-molecule magnets, a dinuclear dysprosium complex, namely [Dy2(L)2(DBM)2(DMF)2]·2DMF (1) was successfully obtained by employing tridentate Schiff base ligand (where H2L = 2-hydroxy-N′’-(2-hydroxy-3-methoxybenzylidene) benzohydrazide), HDBM = dibenzoylmethane, DMF = dimethylformamide). Single-crystal X-ray structural analysis reveals that the key feature of 1 is neutral dinuclear complex, in which two Dy(III) ions with eight-coordinated environment are bridged by two phenoxido oxygen atoms from two Schiff base ligands. Interestingly, complex 1 could be regarded as the structurally related derivatives to our previous reported complex of [Dy2(L)2(DBM)2(DMF)2] (1a) but adding two guest DMF solvents. More importantly, the energy barrier to magnetic relaxation of 1 is slightly higher, with a value of 33 K, when compared to the corresponding complex 1a of 24 K, which provides a good example towards regulating magnetization dynamics in dinuclear dysprosium (III) single-molecule magnets by guest solvent molecules.A novel dinuclear dysprosium complex, [Dy2(L)2(DBM)2(DMF)2]·2DMF (1) (H2L = 2-hydroxy-N′’-(2-hydroxy-3-methoxybenzylidene) benzohydrazide, HDBM = dibenzoylmethane), was synthesized, structurally and magnetically characterized. Interestingly, the energy barrier to magnetic relaxation of 1 is slightly higher, with a value of 33 K, when compared to the corresponding complex 1a [Dy2(L)2(DBM)2(DMF)2] of 24 K, which provides a good example towards regulating magnetization dynamics in dinuclear dysprosium (III) single-molecule magnets by guest solvent molecules.Display Omitted
Keywords: Dinuclear dysprosium complex; Schiff base ligand; Single-molecule magnet;

Upon one-pot reaction of the mono-imine Schiff-base precursor HL 1 (HL 1  = (E)-2-((2-aminophenylimino)methyl)-4,6-di-tert-butyl-phenol), Ni(OAc)2·4H2O and salicylaldehyde, the Ni2 +-template mechanism to the in situ formed nonsymmetrical Salen-type Schiff-base H2L-based complex [Ni(L)] (1) is identified with an intermediate of [Ni(L1)(μ 1-OAc)]. Moreover, within following nonsymmetrical Salen-type Schiff-base Ni2 + complexes, the complex 1 is shown to effectively catalyze the solution polymerization of styrene in the presence of MAO (methylaluminoxane).Through the Ni2 +-template mechanism to nonsymmetrical Salen-type Schiff-base Ni2 + complexes, the representative complex 1 as the catalyst exhibits a good catalytic activity up to 1.03 × 106  g·mol− 1  h− 1 on the solution polymerization of styrene.Display Omitted
Keywords: Ni2 +-template; Nonsymmetrical Salen-type Schiff-base Ni2 + complexes; Polymerization of styrene;

In search of lanthanide single-molecule magnets, a novel dinuclear dysprosium complex, namely [Dy2(L)2(DBM)2(DMF)2]·3CH3OH (1) (H2L = 2-((2-hydroxy-3-methoxybenzylidene)amino)acetic acid, HDBM = dibenzoylmethane), was synthesized, structurally and magnetically characterized. Single-crystal X-ray structural analysis reveals that the key feature of 1 is neutral dinuclear complex, in which two Dy(III) ions with eight-coordinated environment are bridged by two phenoxido oxygen atoms of two o-vanillin Schiff base ligands. Electrospray ionization mass spectrometry (ESI-MS) results revealed that the intact framework of complex 1 stable in methanol solution. Its magnetic susceptibilities to an alternating current revealed that complex 1 exhibits single-molecule magnet behaviour.A novel dinuclear dysprosium complex, [Dy2(L)2(DBM)2(DMF)2]·3CH3OH (1) (H2L = 2-((2-hydroxy-3-methoxybenzylidene)amino)acetic acid, HDBM = dibenzoylmethane), was synthesized, structurally and magnetically characterized. Electrospray ionization mass spectrometry (ESI-MS) results revealed that the intact framework of complex 1 stable in methanol solution. Magnetic susceptibilities to an alternating current revealed that complex 1 exhibits single-molecule magnet behaviour.Display Omitted
Keywords: Dinuclear dysprosium complex; Single-molecule magnet; Electrospray ionization mass spectrometry;

Two novel metal-organic frameworks (MOFs) based on transition metals, namely [Ni(sbdc)(4,4′-bbibp)(H2O)2]n (1) and [Co(sbdc)(4,4′-bbibp)]n (2) (H2sbdc = 4,4′-stilbenedicarboxylic, 4,4′-bbibp = 4,4′-bis(benzoimidazo-1-ly)biphenyl), have been designed and successfully synthesized under solvothermal conditions. Single-crystal X-ray diffraction analysis reveals that complex 1 features a 5-fold classical Ia interpenetrated dia framework with 4-connected (66) sqc6 topology and complex 2 displays a 7-fold classical Ia interpenetrated dia network. Further, the photocatalytic properties of complexes 12 have been investigated. Significantly, the complexes 12 are good photo-catalysts for the degradation of organic dyes (MB/MV/RhB).Two novel Ni(II)/Co(II) CPs have been successfully synthesized, which could be good candidates for the photocatalytic degradation of organic dyes.Display Omitted
Keywords: MOFs; 5-fold and 7-fold interpenetrated frameworks; Photo-catalysts;

Reactivity of cyrhetrenylphosphines: Synthesis and characterization of oxides, boranes and selenides by Diego Sierra; Johana Gomez; Vania Artigas; Mauricio Fuentealba; Andrés Muñoz; A. Hugo Klahn (114-117).
Reaction of cyrhetrenylphosphines, of general formula (η5-C5H4PR2)Re(CO)2L (R = Ph, L = CO (1); R = Cy; L = CO (2); R = Ph, L = PMe3 (3) and R = Ph, L = P(OMe)3 (4)), with H2O2, BH3·THF or selenium gives the respective cyrhetrenylphosphine oxides, boranes and selenides. These species were characterized by standard spectroscopic techniques (FT-IR, 1H and 31PNMR). Based on the 31P― 77Se coupling constant (1 J P-Se) of the phosphine-selenides, we established the following order of basicity of the parent cyrhetrenylphosphine 2  >  3  >  4  >  1. We also confirmed the opposite electronic effects of the cyrhetrenyl and ferrocenyl groups attached to a –PR2 unit. Finally, phosphine selenides 2c and 4c were structurally characterized by X-ray diffraction.New cyrhetrenylphosphine oxides, boranes and selenides were synthesized and characterized. Based on the coupling constant 1 J P-Se of the phosphino selenides the basicity of the cyrhetrenylphosphines was determinate.Display Omitted
Keywords: Cyrhetrenylphosphines; Phosphine oxides; Phosphine-boranes; Phosphine selenides; Basicity;

A inorganic-organic hybrid material constructed from the monolacunary polyoxomolybdates and multi-nuclear copper clusters by Xiao-Yuan Wu; Wen-Bin Yang; Wei-Ming Wu; Jian-Zhen Liao; Sa-Sa Wang; Can-Zhong Lu (118-121).
A novel polyoxometalate (POM)-based inorganic-organic hybrid material constructed from the monolacunary Keggin-type polyoxomolybdates and the multi-nuclear copper clusters, namely, {[Cu8(tz)8(Htz)4(H2O)5][PMo10 VIMoVO39]}∙~10H2O (1) (Htz = 1H-tetrazole) has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectra, PXRD analysis. In 1, the six-nuclear copper clusters in the roof shape were bridged by the tz ligands. These clusters are extended into the wave-like layers by the μ2-Htz ligands and the copper atoms in octahedron coordination geometry. The polyoxomolybdate anions act as the eight-connected node to link the layers into a 3D framework. In addition, the magnetic and photocatalytic properties of compound 1 have been investigated.A novel polyoxometalate (POM)-based inorganic-organic hybrid material constructed from the monolacunary Keggin-type polyoxomolybdates and the multi-nuclear copper clusters, namely, {[Cu8(tz)8(Htz)4(H2O)5][PMo10 VIMoVO39]}∙~10H2O (1) (Htz = 1H–tetrazole) has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectra, PXRD analysis. In compound 1, bridged by the tz ligands, the six-nuclear copper clusters in the roof shape were obtained. These clusters are extended into the wave-like layers by the μ2-Htz ligands and the copper atoms in octahedron coordination geometry. The polyoxomolybdate anions act as the eight-connected node to link the layers into a 3D framework. In addition, the magnetic and photocatalytic properties of compound 1 have been investigated.Display Omitted
Keywords: Polyoxometalate; Multi-nuclear Cu cluster; Inorganic-organic hybrid material; Magnetism; Photocatalytic property;

The synthesis of a silver hexagon using a diiminoisoindoline-based ligand by Ingrid-Suzy Tamgho; Laura A. Crandall; James T. Engle; Christopher J. Ziegler (122-124).
Diiminoisoindoline (DII) can be modified with primary amines to afford bis-substituted heterocycles. Although the metal binding chemistry of isoindoline-based macrocycles and chelates has been explored, the corresponding chemistry of hydrocarbon substituted diiminoisoindolines remains open. The reaction of the bis(benzylimino)isoindoline with AgNO3 affords a Ag6 cluster complexed by four equivalents of ligand. The cluster exhibits a previously unknown argentophilic geometry. The Ag6 unit forms a compressed hexagon, comprised of two Ag3 triangles that are linked together to form a parallelogram. The argentophilic interactions range from ~ 2.76 to ~ 3.17 Å.Display Omitted
Keywords: Diiminoisoindoline; Silver cluster; Argentophilic interaction; Silver hexamer;