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Inorganic Chemistry

Anas Santria, Akira Fuyuhiro, Takamitsu Fukuda, Naoto Ishikawa
A series of heavy lanthanide(III) and yttrium(III) monoporphyrinato complexes formulated in [Ln(TPP)(cyclen)]Cl (Ln = Tb, Dy, Ho, Er, Tm, Yb, and Y; TPP = 5,10,15,20-tetraphenylporphyrinato), with cyclen, 1,4,7,10-tetraazacyclododecane, as a capping ligand, have been prepared in mild conditions and studied using single-crystal X-ray diffraction crystallography. The complexes exhibit an electronic absorption band (B(0,0)) in the range of 421-423 nm, showing a bathochromic shift associated with the increase of the ionic radii of the lanthanide, as well as two peaks of Q(1,0) and Q(0,0) bands between 548-586 nm...
August 14, 2017: Inorganic Chemistry
Qingyun Hu, Congcong Zhuo, Yong Wang, Chuanjiang Hu, Jianping Lang
An m-phthalic diamide-linked bisporphyrin with a benzylamide substituent has been designed and synthesized. It has two types of carbonyl groups. In the solution of this zinc bisporphyrinate, these carbonyl groups are involved in the formation of two different Zn-O coordination interactions: one is formed between neighboring zinc bisporphyrinates; another is formed within zinc bisporphyrinate. The chirality sensing abilities of this zinc porphyrinate to a number of chiral monoamines have been examined. When zinc bisporphyrinate was mixed with a series of chiral monoamines, the signs of the circular dichroism spectra for the chiral monoamines of the same handedness with an aryl group as the substituent are just opposite to those with an alkyl group as the substituent...
August 14, 2017: Inorganic Chemistry
Kankana Mullick, Sourav Biswas, Chiho Kim, Ramamurthy Ramprasad, Alfredo M Angeles-Boza, Steven L Suib
A heterogeneous copper oxide supported on mesoporous manganese oxide (meso Cu/MnOx) was explored for Ullmann-type cross-coupling reactions. An inverse micelle-templated evaporation-induced self-assembly method with in situ addition of copper was adopted to synthesize the mesoporous catalyst. Broad substrate scope and excellent functional group tolerability in C-O, C-N, and C-S bond formation reactions were observed using the optimized reaction conditions. The catalytic protocol was ligand free, and the catalyst was reusable without any significant loss of activity...
August 11, 2017: Inorganic Chemistry
Svetlana V Pershina, Eugenia A Il'ina, Olga G Reznitskikh
The glass-ceramic composite electrolytes based on tetragonal Li7La3Zr2O12 (t-LLZ) and cubic Al-doped Li7La3Zr2O12 (c-LLZ) with the LiPO3 glass additive have been prepared. The electrical conductivity and microstructure of the t-LLZ/LiPO3 and c-LLZ/LiPO3 composites have been investigated. The phase evolution of electrolytes has been studied using XRD, SEM, and Raman spectroscopy. It was indicated that the impurities formation depends on the composition of the composite. The phase composition of the solid electrolytes determines their thermal properties, which have been studied by the DSC method...
August 10, 2017: Inorganic Chemistry
Friederike Adams, Martin R Machat, Peter T Altenbuchner, Johannes Ehrmaier, Alexander Pöthig, Tolga N V Karsili, Bernhard Rieger
Herein, we present a fundamental study of isostructural 2-methoxyethylamino-bis(phenolate)-lanthanide complexes [(ONOO)(R)M(X)(THF)] (M = Lu, Y; R = (t)Bu, CMe2Ph, X = CH2TMS, collidine; THF = tetrahydrofuran; TMS = trimethylsilyl) for rare-earth metal-mediated group-transfer polymerization (GTP). This analysis includes the differentiation of electron-donating and nondonating vinyl monomers and two metal centers with regard to the ionic radius (yttrium and lutetium). In addition, highly nucleophilic alkyl initiators are compared with electron-donating heteroaromatic initiators...
August 10, 2017: Inorganic Chemistry
Wen-Juan Shi, Li-Yun Du, Hong-Yun Yang, Kun Zhang, Lei Hou, Yao-Yu Wang
Three new coordination polymers, {[Mn3(pzbtz)2(Cl)2(H2O)2]·4H2O}n (1), {Mn2(pzbtz)(SO4)(H2O)3]·3H2O}n (2), and {[Mn3(pzbtz)3(H2O)3]·1.5DMA·2H2O}n (3), have been solvothermally synthesized with MnCl2/MnSO4 and a bitriazole ligand, 5'-(pyrazin-2-yl)-2H,4'H-3,3'-bi(1,2,4-triazole) (H2pzbtz), in different solvent systems. H2pzbtz shows different geometrical configurations and coordination modes, leading to the diverse three-dimensional (3D) frameworks of 1-3. Complex 1 contains the trinuclear Mn3(tr)4X2 (X = Cl or H2O) clusters and reveals an unobserved (3,4,8)-connected sqc929 topological framework with two types of cages...
August 10, 2017: Inorganic Chemistry
Yu-Sian Li, Jia-Ling Liao, Ke-Ting Lin, Wen-Yi Hung, Shih-Hung Liu, Gene-Hsiang Lee, Pi-Tai Chou, Yun Chi
Tetradentate chelates bearing tripodal arranged terpyridine and a functional pyrazole unit (i.e., L1-H and L2-H) were employed in preparation of Ir(III) complexes [Ir(L1)Cl2] (1) and [Ir(L2)Cl2] (2); subsequent chloride-to-bipyrazolate substitution gave [Ir(L1)(bipz)] (3) and [Ir(L2)(bipz)] (4). Single-crystal X-ray structural studies on 1 and 3 showed the possession of a tetradentate chelate, whereas the remaining cis-sites are occupied by either dual chlorides or the bipz chelate, respectively. Sky blue organic light-emitting diode with peak efficiencies (10...
August 10, 2017: Inorganic Chemistry
Wenge Xiao, Dan Wu, Liangliang Zhang, Xia Zhang, Zhendong Hao, Guo-Hui Pan, Ligong Zhang, Xuewei Ba, Jiahua Zhang
Forming solid solutions through cation substitution is an efficient way to improve the luminescence properties of Ce(3+) or Eu(2+) activated phosphors and even to develop new ones, which is badly needed for phosphor-converted white LEDs. Here, we report new color tunable solid solution phosphors based on Eu(2+) activated K2Al2B2O7 as a typical case to demonstrate that, besides crystal field splitting of 5d levels, centroid shift and Stokes shift can be dominant in tuning excitation and emission spectra as well as thermal stability of solid solution phosphors, both of which were previously considered to be negligible...
August 10, 2017: Inorganic Chemistry
Bastien Loret, Anne Forget, Jean-Baptiste Moussy, Sylvie Poissonnet, Patrick Bonnaillie, Gaston Collin, Pierre Thuéry, Alain Sacuto, Dorothée Colson
We report an original procedure for the elaboration of very high-quality single crystals of superconducting HgBa2Ca2Cu3O8+δ mercury cuprates. These single crystals are unique, with very high-quality surface paving the way for spectroscopic, transport, and thermodynamic probes in order to understand the hole-doped cuprate phase diagram. Annealing allows one to optimize Tc up to Tc(max) = 133 K. The superconductivity transition width of about 2 K indicates that they are homogeneous. We show for the first time that, with adequate heat treatment, Hg-1223 can be largely underdoped and its doping level controlled...
August 10, 2017: Inorganic Chemistry
Nadia Soulmi, Damien Dambournet, Cécile Rizzi, Juliette Sirieix-Plénet, Mathieu Duttine, Alain Wattiaux, Jolanta Swiatowska, Olaf J Borkiewicz, Henri Groult, Laurent Gaillon
The potential application of high capacity Sn-based electrode materials for energy storage, particularly in rechargeable batteries, has led to extensive research activities. In this scope, the development of an innovative synthesis route allowing to downsize particles to the nanoscale is of particular interest owing to the ability of such nanomaterial to better accommodate volume changes upon electrochemical reactions. Here, we report on the use of room temperature ionic liquid (i.e., [EMIm(+)][TFSI(-)]) as solvent, template, and stabilizer for Sn-based nanoparticles...
August 10, 2017: Inorganic Chemistry
Lukasz Szatkowski, Michael B Hall
Recent experimental work shows that the 18-electron molybdenum complexes (1,2,4-C5H2tBu3)Mo(PMe3)2H3 (Cp(tBu)MoH3) and (C5HiPr4)Mo(PMe3)2H3 (Cp(iPr)MoH3) undergo oxidatively induced reductive elimination of dihydrogen (H2), slowly forming the 15-electron monohydride species in tetrahydrofuran and acetonitrile. The 17-electron [Cp(tBu)MoH3](+) derivative was stable enough to be characterized by X-ray diffraction, while [Cp(iPr)MoH3](+) was not. Density functional theory calculations of the H2 elimination pathways for both complexes in the gas phase and in a continuum solvent model indicate that H2 elimination from [Cp(iPr)MoH3](+) has a lower barrier than that from [Cp(tBu)MoH3](+)...
August 10, 2017: Inorganic Chemistry
Hui-Ting Mao, Chun-Xiu Zang, Guo-Gang Shan, Hai-Zhu Sun, Wen-Fa Xie, Zhong-Min Su
Nondoped electroluminescent devices offer advantages over their doped counterparts such as good reproducibility, reduced phase separation between host and guest materials, and potential of lower-cost devices. However, low luminance efficiencies and significant roll-off values are longstanding issues for nondoped devices, and a rational design strategy for the preparation of efficient phosphors is highly desired. In this work, cyclometalated Ir(III) complexes 3CzIr(mtpy), 4CzIr(mtpy), 3POIr(mtpy), and 4POIr(mtpy) bearing carbazole (Cz) or diphenylphosphoryl (Ph2PO) groups substituted at different positions of 1,2-diphenyl-H-benzimidazole (HPBI) were designed and synthesized...
August 10, 2017: Inorganic Chemistry
Hafiz Muhammad Asif, Yunshan Zhou, Lijuan Zhang, Nusrat Shaheen, Di Yang, Jiaqi Li, Yi Long, Arshad Iqbal, Yanqin Li
Two new porphyrin-polyoxometalate hybrids, namely, [(C4H9)4N]10H2[{COHNC(CH2O)3P2V3W15O59}2C44N4H28]·CH3CN 1, bearing two covalent-bonded Wells-Dawson-type polyoxometalates (POMs), and [(C4H9)4N)]5H[COHNC(CH2O)3P2V3W15O59{C44H29N4}]·CH3CN 2, bearing one covalent-bonded POM, have been synthesized and thoroughly characterized by means of elemental analysis, powder XRD, FT-IR, (1)H ((31)P, (51)V) NMR, MALDI-TOF-MS, UV-vis spectra, and cyclic voltammetry measurement. Experimental results demonstrate that while all the compounds show remarkable third-order optical nonlinearities, the hybrids 1 and 2 are superior to their corresponding porphyrin precursors (molecular second hyperpolarizability γ = 8...
August 10, 2017: Inorganic Chemistry
Papri Sutar, Tapas Kumar Maji
The recent upsurge in research on coordination polymer gels (CPGs) stems from their synthetic modularity, nanoscale processability, and versatile functionalities. Here we report self-assembly of an amphiphilic, tripodal low-molecular weight gelator (L) that consists of 4,4',4-[1,3,5-phenyl-tri(methoxy)]-tris-benzene core and 2,2':6',2″-terpyridyl termini, with different metal ions toward the formation of CPGs that show controllable nanomorphologies, tunable emission, and stimuli-responsive behaviors. L can also act as a selective chemosensor for Zn(II) with very low limit of detection (0...
August 9, 2017: Inorganic Chemistry
Sean N Natoli, Matthias Zeller, Tong Ren
Reported herein is an expanded investigation into a new method for the preparation of Co(III) cyclam bis-alkynyls (cyclam = 1,4,8,11-tetraazacyclotetradecane) under aerobic, weak base conditions. Treatment of trans-[Co(cyclam)(C2Ar)Cl]Cl-type complexes (Ar = C6F5 (1a), 4-C6H4NMe2 (1b)) with AgOTf in MeCN resulted in the doubly charged complexes [Co(cyclam)(C2Ar)(NCMe)](OTf)2 (Ar = C6F5 (2a), 4-C6H4NMe2 (2b)). These solvento complexes 2a,b undergo rapid alkynylation under aerobic conditions in the presence of an organic base and HC2Ar' to form the symmetrical or unsymmetrical bis-alkynyl complexes trans-[Co(cyclam)(C2Ar)(C2Ar')](OTf) (Ar/Ar' = C6F5 (3a), 4-C6H4NMe2 (3b); Ar = C6F5 and Ar' = 4-C6H4NMe2 (3c), C2Ph (3d)) in good yields...
August 9, 2017: Inorganic Chemistry
Ram Krishna Hona, Ashfia Huq, Suresh Mulmi, Farshid Ramezanipour
The ability to control electrical properties and magnetism by varying the crystal structure using the effect of the A-site cation in oxygen-deficient perovskites has been studied in AA'Fe2O6-δ, where A = Sr, Ca and A' = Sr. The structure of Sr2Fe2O6-δ, synthesized at 1250 °C in air, contains dimeric units of FeO5 square pyramids separated by FeO6 octahedra. Here we show that this ordering scheme can be transformed by changing the A-site cations from Sr to Ca. This leads to a structure where layers of corner-sharing FeO6 octahedra are separated by chains of FeO4 tetrahedra...
August 9, 2017: Inorganic Chemistry
Anindita Chakraborty, Subhajit Laha, Kesavan Kamali, Chandrabhas Narayana, Muthusamy Eswaramoorthy, Tapas Kumar Maji
Self-assembly of metal-organic framework (MOF) nanoparticles (NPs) with a functional material can result in MOF nanocomposites having new and advanced properties along with the fabrication of new nanoscopic structures. However, such assembly of MOFs has not been realized to date. Here we report self-assembled nanocomposites of the zeolitic imidazolate framework (ZIF-8) and layered aminoclay (AC) for the first time, and the ZIF-8@AC composites exhibit significantly enhanced adsorption properties in comparison to those of pristine ZIF-8 nanoparticles...
August 9, 2017: Inorganic Chemistry
Aarón Torres-Huerta, Miriam de J Velásquez-Hernández, Lillian G Ramírez-Palma, Fernando Cortés-Guzmán, Diego Martínez-Otero, Uvaldo Hernández-Balderas, Vojtech Jancik
A series of borosilicates was synthesized, where the structure of the borosilicate core was easily modulated using two strategies: blocking of condensation sites and controlling the stoichiometry of the reaction. Thus, on the one hand, the condensation of phenylboronic or 3-hydroxyphenylboronic acid with diacetoxysilylalkoxide [((t)BuO)(Ph3CO)Si(OAc)2] led to the formation of borosilicates ((t)BuO)(Ph3CO)Si{(μ-O)BPh}2(μ-O) (1), [{((t)BuO)(Ph3CO)Si(μ-O)BPh(μ-O)}2] (2), and [{((t)BuO)(Ph3CO)Si(μ-O)B(3-HOPh)(μ-O)}2] (3) with a cyclic inorganic B2SiO3 or B2Si2O4 core, respectively...
August 9, 2017: Inorganic Chemistry
Baisheng Sa, Honglei Yang, Naihua Miao, Kangming Hu, Jian Zhou, Bo Wu, Zhimei Sun
Tc-based oxides are of interest because of their complex crystalline structures. In this work, the phonon dispersions, lattice distortions, and elastic constants of TcO2 at external pressures up to 120 GPa were comprehensively studied using first-principles calculations. It is found that the lattice dynamic stability of TcO2 can be assessed by fitting the Γ-Z acoustical phonon branch. The applied external pressure can be divided into three ranges: the low-pressure stable range, the middle-pressure buckling range, and the high-pressure unstable range...
August 9, 2017: Inorganic Chemistry
Blaž Alič, Melita Tramšek, Anton Kokalj, Gašper Tavčar
The recently prepared novel naked fluoride reagent 1,3-bis(2,6-diisopropylphenyl)imidazolium fluoride ([(L(Dipp))H][F]), treated with an excess of MF4 (M = Si, Ge), results in isolation of [(L(Dipp))H][MF5] products with the elusive trigonal bipyramidal MF5(-) anions. Specific steric characteristics of the [(L(Dipp))H](+) cation readily support isolation of monomeric and discrete trigonal bipyramidal fluorido anions of silicon and germanium. Based on combination of experimental results and DFT calculations, we demonstrate that the role of bulky cation is not solely due to steric hindering but also due to electrostatic effects, which are important in the design of such uncommon species...
August 9, 2017: Inorganic Chemistry
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