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Inorganic Chemistry

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https://www.readbyqxmd.com/read/29350928/a-comparative-investigation-of-proton-conductivities-for-two-metal-organic-frameworks-under-water-and-aqua-ammonia-vapors
#1
Ruilan Liu, Lili Zhao, Wei Dai, Chenglin Yang, Xi Liang, Gang Li
Our investigation on the proton conductivities of two water-stable isostructural 3D Co(II) MOFs, {[Co3(DMPhIDC)2(H2O)6]·2H2O}n (1) [DMPhH3IDC = 2-(3,4-dimethylphenyl)-imidazole-4,5-dicarboxylic acid] and {[Co3(m-BrPhIDC)2(H2O)6]·2H2O} (2) [m-BrPhH3IDC = 2-(m-bromophenyl)-imidazole-4,5-dicarboxylic acid], under water or aqua-ammonia vapor shows that the optimized proton conductivities of both 1 and 2 under aqua-ammonia vapor are 4.41 × 10-3 S·cm-1 and 5.07 × 10-4 S·cm-1 (at aqua-ammonia vapor from 1.5 M NH3·H2O solution and 100 °C), respectively, which are approximately 1 order of magnitude greater than those maximum values (8...
January 19, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29350924/influences-of-bifunctional-pnp-pincer-ligands-on-low-valent-cobalt-complexes-relevant-to-co2-hydrogenation
#2
Matthew R Mills, Charles L Barnes, Wesley H Bernskoetter
Pincer ligated coordination complexes bearing bifunctional sites have been at the center of recent developments in reversible hydrogenation catalysis, especially in cases utilizing base metals. The influence of bifunctional ligands on low valent cobalt complexes is detailed here using comparisons between the PNP-pincer ligands MeN[CH2CH2(PR2)]2 and HN[CH2CH2(PR2)]2 (R = iPr, Cy). Comparative catalytic studies of CO2 hydrogenation show that cobalt(I) precatalysts bearing the tertiary amine ligand dramatically outperform those bearing the secondary amine pincer ligand...
January 19, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29350026/steric-and-acidity-control-in-hydrogen-bonding-and-proton-transfer-to-trans-w-n2-2-dppe-2
#3
Nikolay V Kireev, Oleg A Filippov, Alexander A Pavlov, Lina M Epstein, Victor D Makhaev, Victor P Dyadchenko, Elena S Shubina, Natalia V Belkova
The interaction of trans-W(N2)2(dppe)2 (1; dppe = 1,2-bis(diphenylphosphino)ethane) with relatively weak acids (p-nitrophenol, fluorinated alcohols, CF3COOH) was studied by means of variable temperature IR and NMR spectroscopy and complemented by DFT/B3PW91-D3 calculations. The results show, for the first time, the formation of a hydrogen bond to the coordinated dinitrogen, W-N≡N···H-O, that is preferred over H-bonding to the metal atom, W···H-O, despite the higher proton affinity of the latter. Protonation of the core metal-the undesirable side step in the conversion of N2 to NH3-can be avoided by using weaker and, more importantly, bulkier acids...
January 19, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29345923/capped-polyoxometalate-pillars-between-metal-organic-layers-for-transferring-a-supramolecular-structure-into-a-covalent-3d-framework
#4
Yu-Jie Wang, Yang-Yang Zhou, Hong-Guo Hao, Man Song, Na Zhang, Shuang Yao, Jing-Hui Yan, Zhi-Ming Zhang, Tong-Bu Lu
Two robust metal-organic frameworks (MOFs), {H4[Ni(π-H2O)2]2[Ni(rt-H2O)2]8Ni4(Tri)24}[VIVW12O40]2·24H2O (1) and {H[Ni(π-O)2]2[Ni(rt-H2O)2]8Ni4(Tri)24}[VIVW10VV2O40V2][VIVW9VV3O40VIV2]·24H2O (2) (Tri = 1,2,4-triazole), composed of polyoxometalates (POMs) and metal-organic units, were designed and synthesized by a hydrothermal method. Structure analysis indicates that there is a metal-organic crown [{Ni3(Tri)6(H2O)4}4] ({Ni12}) in these two compounds. In 1, the {Ni12} crown embraces four pendant Tri ligands that could capture a cationic [Ni(H2O)2]2+ group, resulting in the Ni13-Tri building unit [Ni(H2O)2{Ni3(Tri)6(H2O)4}4] ({Ni13})...
January 18, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29345469/a-large-family-of-centrosymmetric-and-chiral-f-element-bearing-iodate-selenates-exhibiting-coordination-number-and-dimensional-reductions
#5
Meiying Qie, Jian Lin, Fang Kong, Mark A Silver, Zenghui Yue, Xiaomei Wang, Linjuan Zhang, Hongliang Bao, Thomas E Albrecht-Schmitt, Jian-Qiang Wang
The exploration of phase formation in the f-element-bearing iodate selenate system has resulted in 14 novel rare-earth-containing iodate selenates, Ln(IO3)(SeO4) (Ln = La, Ce, Pr, Nd; LnISeO-1), Ln(IO3)(SeO4)(H2O) (Ln = Sm, Eu; LnISeO-2), and Ln(IO3)(SeO4)(H2O)2·H2O (Ln = Gd, Dy, Ho, Er, Tm, Yb, Lu, Y; LnISeO-3), as well as two new thorium iodate selenates, Th(OH)(IO3)(SeO4)(H2O) (ThISeO-1) and Th(IO3)2(SeO4) (ThISeO-2). LnISeO-3 and ThISeO-2 crystallize in the chiral space group P212121, while LnISeO-1, LnISeO-2, and ThISeO-1 crystallize in the centrosymmetric space group P21/c...
January 18, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29345462/fluorescent-zn-pdc-tb3-coordination-polymer-nanostructure-a-candidate-for-highly-selective-detections-of-cefixime-antibiotic-and-acetone-in-aqueous-system
#6
Hong Pan, Sufan Wang, Xiaoyao Dao, Yonghong Ni
Tb3+-doped zinc-based coordination polymer nanospindle bundles (Zn-PDC/Tb3+, or [Zn(2,5-PDC)(H2O)2]·H2O/Tb3+) were synthesized by a simple solution precipitation route at room temperature, employing Zn(NO3)2, Tb(NO3)3, and 2,5-Na2PDC as the initial reactants, and a mixture of water and ethanol with the volume ratio of 10:10 as the solvent. The as-obtained nanostructures presented strong fluorescent emission under the excitation of 298 nm light, which was attributed to the characteristic emission of the Tb3+ ion...
January 18, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29341598/a-joint-strategy-to-evaluate-the-microscopic-origin-of-the-second-harmonic-generation-response-in-nonpolar-abco3f-compounds
#7
Qun Jing, Guang Yang, Zhaohui Chen, Xiaoyu Dong, Yunjing Shi
In this paper, a joint strategy was proposed to investigate the microscopic origin of the second-harmonic-generation (SHG) response in nonpolar ABCO3F compounds. The SHG coefficients of ABCO3F were evaluated using finite-field and sum-over-states methods. The tendency of the obtained SHG tensors is in good agreement with the powder SHG response. The atomic contribution was investigated using variation of the atomic charges and bandwidth of occupied atomic states. The results show that oxygen states play a key role in determining the SHG response, and the neighboring divalent cations exert a indirect influence via covalent interaction...
January 17, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29338216/effect-of-thermochemical-synthetic-conditions-on-the-structure-and-dielectric-properties-of-ga1-9fe0-1o3-compounds
#8
Swadipta Roy, C V Ramana
We report on the tunable and controlled dielectric properties of iron (Fe)-doped gallium oxide (Ga2O3; Ga1.9Fe0.1O3, referred to as GFO) inorganic compounds. The GFO materials were synthesized using a standard high-temperature, solid-state chemical reaction method by varying the thermochemical processing conditions, namely, different calcination and sintering environments. Structural characterization by X-ray diffraction revealed that GFO compounds crystallize in the β-Ga2O3 phase. The Fe doping has induced slight lattice strain in GFO, which is evident in structural analysis...
January 17, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29337539/a-comparative-irmpd-and-dft-study-of-fe3-and-uo22-complexation-with-n-methylacetohydroxamic-acid
#9
Thibault Terencio, Jana Roithová, Stéphane Brandès, Yoann Rousselin, Marie-José Penouilh, Michel Meyer
Iron(III) and uranyl complexes of N-methylacetohydroxamic acid (NMAH) have been investigated by mass spectrometry, infrared multiphoton dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations. A comparison between IRMPD and theoretical IR spectra enabled one to probe the structures for some selected complexes detected in the gas phase. The results show that coordination of Fe3+ and UO22+ by hydroxamic acid is of a very similar nature. Natural bond orbital analysis suggests that bonding in uranyl complexes possesses a slightly stronger ionic character than that in iron complexes...
January 16, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29336572/-hg-scn-3-2-%C3%AE-l-2-an-efficient-secondary-building-unit-for-the-synthesis-of-2d-iron-ii-spin-crossover-coordination-polymers
#10
Daopeng Zhang, Francisco Javier Valverde-Muñoz, Carlos Bartual-Murgui, Lucía Piñeiro-López, M Carmen Muñoz, José Antonio Real
We report an unprecedented series of two-dimensional (2D) spin-crossover (SCO) heterobimetallic coordination polymers generically formulated as {FeII[(HgII(SCN)3)2](L)x}·Solv, where x = 2 for L = tvp (trans-(4,4'-vinylenedipyridine)) (1tvp), bpmh ((1E,2E)-1,2-bis(pyridin-4-ylmethylene)hydrazine) (1bpmh·nCH3OH; n = 0, 1), bpeh ((1E,2E)-1,2-bis(1-(pyridin-4-yl)ethylidene)hydrazine) (1bpeh·nH2O; n = 0, 1) and x = 2.33 for L = bpbz (1,4-bis(pyridin-4-yl)benzene) (1bpbz·nH2O; n = 0, 2/3). The results confirm that self-assembly of FeII, [HgII(SCN)4]2-, and ditopic rodlike bridging ligands L containing 4-pyridyl moieties favors the formation of linear [Fe(μ-L)]n2n+ chains and in situ generated binuclear units {[HgII(SCN)3]2(μ-L)}2-...
January 16, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29336570/design-of-near-infrared-luminescent-lanthanide-complexes-sensitive-to-environmental-stimulus-through-rationally-tuning-the-secondary-coordination-sphere
#11
Yingying Ning, Yi-Wei Liu, Yin-Shan Meng, Jun-Long Zhang
The design of near-infrared (NIR) emissive lanthanide (Ln) complexes sensitive to external stimulus is fundamentally important for the practical application of Ln materials. Because NIR emission from Ln is extremely sensitive to X-H (X = C, N and O) bond vibration, we herein report to harness the secondary coordination sphere to design NIR luminescent lanthanide sensors. Toward this goal, we designed and synthesized two isomeric [(η5-C5H5)Co{(D3CO)2P = O}3]-Yb(III)-7,8,12,13,17,18-hexafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porpholactol NIR emitters, Yb-up and Yb-down, based on the stereoisomerism of porphyrin peripheral β-hydroxyl group...
January 16, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29336566/electrochemistry-of-bis-pyridine-cobalt-nitrophenyl-corroles-in-nonaqueous-media
#12
Xiaoqin Jiang, Mario L Naitana, Nicolas Desbois, Valentin Quesneau, Stéphane Brandès, Yoann Rousselin, Wenqian Shan, W Ryan Osterloh, Virginie Blondeau-Patissier, Claude P Gros, Karl M Kadish
A series of bis(pyridine)cobalt corroles with one or three nitrophenyl groups on the meso positions of the corrole macrocycle were synthesized and characterized as to their electrochemical and spectroscopic properties in dichloromethane, benzonitrile, and pyridine. The potentials for each electrode reaction were measured by cyclic voltammetry and the electron-transfer mechanisms evaluated by analysis of the electrochemical data combined with UV-visible spectra of the neutral, electroreduced, and electroxidized forms of the corroles...
January 16, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29336563/electron-precise-group-5-dimetallaheteroboranes-cpv-%C3%AE-eph-2-%C3%AE-%C3%AE-2-%C3%AE-2-bh3e-and-cpnb-%C3%AE-eph-2-%C3%AE-%C3%AE-2-%C3%AE-2-b2h4e-e-s-or-se
#13
Monojit Ghosal Chowdhury, Subrat Kumar Barik, Koushik Saha, Bakthavachalam Kirubakaran, Abhishek Banerjee, Venkatachalam Ramkumar, Sundargopal Ghosh
Synthesis and structural elucidation of various electron precise group 5 dimetallaheteroboranes have been described. Room temperature reaction of [Cp2VCl2] with Li[BH3(EPh)], generated from the treatment of LiBH4·THF and Ph2E2 (E = S or Se), for 1 h in toluene, followed by thermolysis, led to the formation of bimetallic complexes [{CpV(μ-EPh)}2{μ-η2:η2-BH3E}], 1 and 2 (1: E = S and 2: E = Se), and [{CpV(μ-SePh)}2{μ-η2:η2-BH(OC4H8)Se}], 3. One of the striking features of these compounds is that they represent a rare class of distorted tetrahedral clusters having bridging hydrogens...
January 16, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29336561/a-borane-platinum-complex-undergoing-reversible-hydride-migration-in-solution
#14
Abdollah Neshat, Hamid R Shahsavari, Piero Mastrorilli, Stefano Todisco, Mohsen Golbon Haghighi, Behrouz Notash
Reaction of [Pt(κ2-C,N-ppy)(dmso)Cl], 1 (Hppy = 2-phenylpyridine), with Na[H2B(mb)2] (Hmb = 2-mercapto-benzimidazole) smoothly afforded the complex {[(κ3-S,B,S-HB(mb)2]Pt(κ2-C,N-ppy)H}, 2, featuring a strong reverse-dative Pt → B σ interaction in the solid state. When dissolved in thf (or acetone) solution, 2 undergoes a reversible Pt-H bond activation, establishing an equilibrium between the hexacoordinated 2 and the tetracoordinate complex {[(κ2-S,S-H2B(mb)2]Pt(κ2-C,N-ppy)}, 3, as ascertained by multinuclear NMR...
January 16, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29336560/trifluoromethyl-substituted-iridium-iii-complexes-from-photophysics-to-photooxidation-of-a-biological-target
#15
Robin Bevernaegie, Lionel Marcélis, Baptiste Laramée-Milette, Julien De Winter, Koen Robeyns, Pascal Gerbaux, Garry S Hanan, Benjamin Elias
Photodynamic therapeutic agents are of key interest in developing new strategies to develop more specific and efficient anticancer treatments. In comparison to classical chemotherapeutic agents, the activity of photodynamic therapeutic compounds can be finely controlled thanks to the light triggering of their photoreactivity. The development of type I photosensitizing agents, which do not rely on the production of ROS, is highly desirable. In this context, we developed new iridium(III) complexes which are able to photoreact with biomolecules; namely, our Ir(III) complexes can oxidize guanine residues under visible light irradiation...
January 16, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29336559/investigation-on-two-forms-of-temperature-sensing-parameters-for-fluorescence-intensity-ratio-thermometry-based-on-thermal-coupled-theory
#16
Mochen Jia, Guofeng Liu, Zhen Sun, Zuoling Fu, Weiguo Xu
Absolute temperature sensitivity (Sa) reflects the precision of sensors that belong to the same mechanism, whereas relative temperature sensitivity (Sr) is used to compare sensors from different mechanisms. For the fluorescence intensity ratio (FIR) thermometry based on two thermally coupled energy levels of one rare earth (RE) ion, we define a new ratio as the temperature-sensing parameter that can vary greatly with temperature in some circumstances, which can obtain higher Sa without changing Sr. Further discussion is made on the conditions under which these two forms of temperature-sensing parameters can be used to achieve higher Sa for biomedical temperature sensing...
January 16, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29336558/excited-state-processes-of-cyclometalated-platinum-ii-charge-transfer-dimers-bridged-by-hydroxypyridines
#17
Arnab Chakraborty, James E Yarnell, Roger D Sommer, Subhangi Roy, Felix N Castellano
A series of four anti-disposed dinuclear platinum(II) complexes featuring metal-metal-to-ligand charge-transfer (MMLCT) excited states, bridged by either 2-hydroxy-6-methylpyridine or 2-hydroxy-6-phenylpyridine and cyclometalated with 7,8-benzoquinoline or 2-phenylpyridine, are presented. The 2-hydroxypyridine bridging ligands control intramolecular d8-d8 metal-metal σ interactions, affecting the frontier orbitals' electronic structure, resulting in marked changes to the ground- and excited-state properties of these complexes...
January 16, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29328648/two-step-synthesis-and-surface-modification-of-caznos-mn2-phosphors-and-the-fabrication-of-a-luminescent-poly-dimethylsiloxane-film
#18
Zihan Xu, Zhiguo Xia, Quanlin Liu
The CaZnOS:Mn2+ (CZOSM) phosphor has been extensively studied for its excellent optical performance, with a typical red emission band peaking at about 580 nm ascribed to the 4T1(4G)-6A1(6S) transition of Mn2+. Herein the CZOSM phosphor was synthesized by a novel two-step method accompanied by control of the morphology of the precursor in the first step followed by sintering in the second step, which demonstrated improved emission intensity and uniform morphology simultaneously compared to those obtained by the traditional solid-state reaction route...
January 12, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29327923/aliovalent-cation-substitution-in-uo2-electronic-and-local-structures-of-u1-ylayo2%C3%A2-x-solid-solutions
#19
Damien Prieur, Laura Martel, Jean-François Vigier, Andreas C Scheinost, Kristina O Kvashnina, Joseph Somers, Philippe M Martin
For nuclear fuel related applications, the oxygen stoichiometry of mixed oxides U1-yMyO2±x is an essential property as it affects fuel properties and may endanger the safe operation of nuclear reactors. A careful review of the open literature indicates that this parameter is difficult to assess properly and that the nature of the defects, i.e., oxygen vacancies or UV, in aliovalent cation-doped UO2 is still subject to controversy. To confirm the formation of UV, we have investigated the room-temperature stable U1-yLayO2±x phase using several experimental methods (e...
January 12, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29327922/a-constrained-tetrapeptide-as-a-model-of-cu-i-binding-sites-involving-cu4s6-clusters-in-proteins
#20
Edit Mesterházy, Colette Lebrun, Attila Jancsó, Pascale Delangle
Peptide design is an efficient strategy to create relevant models of natural metal binding sites found in proteins. The two short tetrapeptides Ac-Cys-dPro-Pro-Cys-NH2 (CdPPC) and Ac-Cys-Pro-Gly-Cys-NH2 (CPGC) were synthesized and studied as mimics of Cu(I) binding sites involved in Cu homeostasis. Both sequences contain β turn inducing motifs to rigidify the peptide backbone structure and thereby preorganize the metal-binding side chains. The more constrained structure of the peptide CdPPC with respect to CPGC was evidenced by the measurements of the temperature coefficients of the amide protons by 1H NMR, which suggest a solvent-shielded intramolecular hydrogen bond in CdPPC, and no H-bond in CPGC...
January 12, 2018: Inorganic Chemistry
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