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Dalton Transactions: An International Journal of Inorganic Chemistry

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https://www.readbyqxmd.com/read/29144523/protein-templated-gold-nanoparticle-synthesis-protein-organization-controlled-gold-sequestration-and-unexpected-reaction-products
#1
Cassidy Hart, Nouf Abuladel, Madeleine Bee, Megan C Kreider, Alexander C CVitan, Moira M Esson, Andrew Farag, Trisha Ibeh, Eleni N Kalivas, Daniel-Mario Larco, Andrew Walker Long, Loukas Lymperopoulos, Zachary Mendel, Nancy Miles, Carly M Zareba, James C Schwabacher, Helen Slucher, Javier Vinals, John M Heddleston, Wenyue Li, Douglas M Fox, Matthew R Hartings
Emerging applications that exploit the properties of nanoparticles for biotechnology require that the nanoparticles be biocompatible or support biological recognition. These types of particles can be produced through syntheses that involve biologically relevant molecules (proteins or natural extracts, for example). Many of the protocols that rely on these molecules are performed without a clear understanding of the mechanism by which the materials are produced. We have investigated a previously described reaction in which gold nanoparticles are produced from the reaction of chloroauric acid and proteins in solution...
November 16, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29143834/cobalt-nickel-and-iron-complexes-of-8-hydroxyquinoline-di-2-picolyl-amine-for-light-driven-hydrogen-evolution
#2
Nadia Alessandra Carmo Dos Santos, Mirco Natali, Elena Badetti, Klaus Wurst, Giulia Licini, Cristiano Zonta
Novel cobalt, nickel, and iron complexes based on the pentadentate 8-hydroxyquinoline-di(2-picolyl)amine ligand were synthesized and thoroughly characterized. X-ray structures of both the cobalt and iron complexes were also obtained, showing the tendency to adopt a pseudo-octahedral geometry by coordination of an additional sixth ligand. These metal complexes were then studied as potential hydrogen-evolving catalysts (HECs) under both electrochemical and light-driven conditions. In particular, two different photochemical systems were tested involving either Ru(bpy)3(2+)/ascorbic acid or Ir(ppy)2(bpy)(+)/TEA sensitizer/sacrificial donor couples...
November 16, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29143826/redox-non-innocent-bis-2-6-diimine-pyridine-ligand-iron-complexes-as-anolytes-for-flow-battery-applications
#3
Gabriel M Duarte, Jason D Braun, Patrick K Giesbrecht, David E Herbert
Diiminepyridines are a well-known class of "non-innocent" ligands that confer additional redox activity to coordination complexes beyond metal-centred oxidation/reduction. Here, we demonstrate that metal coordination complexes (MCCs) of diiminepyridine (DIP) ligands with iron are suitable anolytes for redox-flow battery applications, with enhanced capacitance and stability compared with bipyridine analogs, and access to storage of up to 1.6 electron equivalents. Substitution of the ligand is shown to be a key factor in the cycling stability and performance of MCCs based on DIP ligands, opening the door to further optimization...
November 16, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29143054/amidoboranes-of-rubidium-and-caesium-the-last-missing-members-of-the-alkali-metal-amidoborane-family
#4
Rafał Owarzany, Tomasz Jaroń, Piotr J Leszczyński, Karol J Fijalkowski, Wojciech Grochala
We report the synthesis and physicochemical characterization of two ammonia borane derivatives: rubidium amidoborane (RbNH2BH3) and caesium amidoborane (CsNH2BH3). Both compounds undergo solid-solid phase transition upon heating and then evolve pure hydrogen at temperatures lower than 125 °C. The phase transition is clearly seen in the Raman spectra. We present crystal structures of both low- and high-temperature forms of the title compounds which were solved from powder X-ray data.
November 16, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29143044/electrocatalytic-oxygen-evolution-with-a-cobalt-complex
#5
Hua-Tian Shi, Xiu-Xiu Li, Fang-Hui Wu, Wei-Bin Yu
The development of an earth-abundant, first-row water oxidation catalyst that operates at a high TOF and a low overpotential remains a fundamental chemical challenge. Cobalt complexes are important members of water oxidation catalysts. Herein, we report a cobalt-based robust homogeneous water oxidation catalyst, which can electrocatalyze water oxidation at a high pH and a low overpotential (η = 520 mV) in phosphate buffer. This homogeneous system exhibits a high turnover frequency (about 5 s(-1)) of catalyzing water oxidation to produce oxygen at η = 720 mV...
November 16, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29143014/synthesis-characterization-and-anticancer-activity-of-two-mixed-ligand-copper-ii-complexes-by-regulating-the-vegf-vegfr2-signaling-pathway
#6
Xiu-Ying Qin, Ya-Nan Wang, Xin-Ping Yang, Juan-Juan Liang, Ji-Lin Liu, Zhao-Hui Luo
The single crystals of two novel mixed-ligand copper(ii)-based complexes were obtained and characterized. These complexes can remarkably induce apoptosis, inhibit proliferation, suppress migration and metastasis, and inhibit angiogenesis to inhibit the growth of cervical cancer by down-regulating the expressions of the important proteins FAK, Akt and Erk1/2 or their phosphorylated proteins p-FAK, p-Akt, and p-Erk1/2 downstream of the VEGF/VEGFR2 signaling pathway.
November 16, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29140393/magneto-structural-correlation-of-hexakis-dmso-cobalt-ii-complex
#7
Hiroshi Sakiyama, Reiji Sudo, Takaaki Abiko, Daisuke Yoshioka, Ryoji Mitsuhashi, Masataka Omote, Masahiro Mikuriya, Megumi Yoshitake, Masayuki Koikawa
The magnetostructural correlation of the hexakis-dmso cobalt(ii) complex, [Co(dmso)6](BPh4)2 (dmso: dimethylsulfoxide), was investigated by single-crystal X-ray diffraction study and magnetic measurements. The magnetic analysis concluded the negative Δ value (H = Δ(L - 2/3) + E(L - L) - (3/2)κλL·S + β[-(3/2)κLu + geSu]·Hu (u = x, y, z)), and this was explained by the tetragonal elongation of the octahedral geometry. The magnetostructural correlation was ascertained by both the angular overlap model calculation and the density functional theory calculation...
November 15, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29139510/crystal-structures-and-magnetic-properties-of-two-series-of-phenoxo-o-bridged-dinuclear-ln2-ln-gd-tb-dy-complexes
#8
Marek Machata, Radovan Herchel, Ivan Nemec, Zdeněk Trávníček
Six dinuclear lanthanide compounds of the formulae [Ln2(3m-L4)2(L2)2(MeOH)2]·6MeOH (Ln = Gd - 1a, Tb - 1b, and Dy - 1c) and [Ln2(3m-L4)2(L2)2(DMF)2] (Ln = Gd - 2a, Tb - 2b, and Dy - 2c; DMF = N,N-dimethylformamide, H23m-L4 = (2-[(E)-(3-metoxysalicylidene)amino]phenol), and HL2 = 1,3-diphenyl-1,3-diketopropane) were prepared and characterized by elemental analysis, FTIR spectroscopy, thermogravimetric measurements, single-crystal X-ray structural analysis, and magnetometry, and Gd2 and Dy2 compounds by ab initio methods as well...
November 15, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29139503/formation-of-a-spiro-compound-via-coupling-of-a-cyclopentadienyl-ligand-with-a-diene-moiety-of-titanacyclopentadiene
#9
Masayoshi Bando, Yuki Mizukami, Kiyohiko Nakajima, Zhiyi Song, Tamotsu Takahashi
The treatment of titanacyclopentadienes with bismuth(iii) chloride gave spiro compounds in moderate yields. Two carbon atoms of the diene moiety of the titanacyclopentadiene were connected to one carbon atom of the Cp ligand. This is in sharp contrast to the formation of dihydroindene derivatives, where two carbon-carbon bonds were formed between the diene moiety and the adjacent two carbon atoms of the Cp ligand.
November 15, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29138778/dual-phosphorescence-emission-of-dinuclear-platinum-ii-complex-incorporating-cyclometallating-pyrenyl-dipyridine-based-ligand-and-its-application-in-near-infrared-solution-processed-polymer-light-emitting-diodes
#10
Zhaoran Hao, Fanyuan Meng, Pu Wang, Yafei Wang, Hua Tan, Yong Pei, Shijian Su, Yu Liu
Two novel mono- and binuclear cyclometalated platinum(ii) complexes of (BuPyrDPy)Pt(dpm) and (BuPyrDPy)[Pt(dpm)]2 incorporating a pyrenyl-dipyridine-based cyclometalated ligand were synthesized and characterized, respectively. Single-crystal X-ray diffraction of the two materials revealed each complex's coordination mode; their photophysical, electrochemical as well as electroluminescent properties were also investigated. Both complexes exhibited good solubility and excellent thermal stability. (BuPyrDPy)[Pt(dpm)]2 presented dual phosphorescence emissive character at room-temperature and showed an increased quantum efficiency compared to that of (BuPyrDPy)Pt(dpm)...
November 15, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29138774/exploring-the-effect-of-substituent-in-the-hydrazone-ligand-of-a-family-of-%C3%AE-oxidodivanadium-v-hydrazone-complexes-on-structure-dna-binding-and-anticancer-activity
#11
Debashis Patra, Subhabrata Paul, Indira Majumder, Nayim Sepay, Sachinath Bera, Rita Kundu, Michael G B Drew, Tapas Ghosh
The reaction of 2-hydroxybenzoylhydrazine (H2bh) separately with equimolar amounts of [V(IV)O(aa)2] and [V(IV)O(ba)2] in CHCl3 afforded the complexes [VO3(HL(1))2] (1) and [VO3(HL(2))2] (2) respectively in good to excellent yield ((HL(1))(2-) and (HL(2))(2-) represent respectively the dianionic form of 2-hydroxybenzoylhydrazones of acetylacetone (H3L(1)) and benzoylacetone (H3L(2)) (general abbreviation H3L)). From X-ray structure analysis, the V(V)-O-V(V) angle was found to be ∼115° and 180° in 1 and 2 respectively...
November 15, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29138772/mesoporous-silica-nanoparticles-incorporating-squaraine-based-photosensitizers-a-combined-experimental-and-computational-approach
#12
Ivana Miletto, Alberto Fraccarollo, Nadia Barbero, Claudia Barolo, Maurizio Cossi, Leonardo Marchese, Enrica Gianotti
Squaraine dyes, that exhibit intense absorption in the red/near infrared region, have been successfully introduced into mesoporous silica nanoparticles (MSNs) to obtain a nanoplatform for photodynamic therapy. Three brominated squaraine dyes which exhibited good PS performance in solution but a different behaviour in vitro due to cell permeability issues were used as photosensitizers. The effects of the adsorption within the pores of MSNs on the overall UV-Vis-NIR absorption and emission properties as well as on the PS performance was evaluated via a combined experimental and computational physico-chemical approach, which allowed us to correlate the unusual optical properties of two out of three systems with the dimerization of squaraines on the silica surface, with detrimental effects on the PS performance...
November 15, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29138771/near-infrared-aza-bodipy-fluorescent-probe-for-selective-cu-2-detection-and-its-potential-in-living-cell-imaging
#13
Yordkhuan Tachapermpon, Sopida Thavornpradit, Adisri Charoenpanich, Jitnapa Sirirak, Kevin Burgess, Nantanit Wanichacheva
A near-infrared (NIR) fluorescent sensor 1 composed of an aza-boron-dipyrromethene (aza-BODIPY) core covalently bound to two di-2-picolylamine moieties was conceived for Cu(2+) detection in aqueous solutions. Spectroscopic properties and binding abilities with several metal ions were investigated in phosphate buffered saline (pH 7.4): acetonitrile (95 : 5 v/v) with Triton X-100 via fluorometric titrations. The fluorescence of sensor 1 was quenched selectively by cupric ions in the presence of alkali- and transition-metal-ions...
November 15, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29138768/the-role-of-trinuclear-species-in-a-palladium-acetate-trifluoroacetic-acid-catalytic-system
#14
Jiří Váňa, Jan Lang, Mária Šoltésová, Jiří Hanusek, Aleš Růžička, Miloš Sedlák, Jana Roithová
Reactions catalyzed by palladium(ii) acetate and trifluoroacetic acid (TFA) have a clear preactivation phase. However, the structure of real catalytic species remains unclear. We show that the key species are cyclic trinuclear complexes of composition [Pd3(OAc)6-x(OTFA)x] (x = 1-6) formed by a sequential ligand exchange from [Pd3(OAc)6]. Furthermore, we prove that the trinuclear palladium backbone of the precatalyst remains preserved during the first phase of the C-H activation reaction of acetanilides. In other words, the reaction pathway including the trinuclear species should be taken into account in discussion about mechanisms of the reactions catalyzed by palladium acetates...
November 15, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29138766/imidazole-stabilized-electron-deficient-boron-cations
#15
Kaoko Sato, Tristan Tsai Yuan Tan, Felix Schäfers, F Ekkehardt Hahn, Douglas W Stephan
The borenium cations [(C7H5N2Ad)B(C6F5)2][AlCl4/Al2Cl7] 2a, and [(C7H5N2Me)B(C6F5)2][B(C6F5)4] 2b were prepared and are shown to feature a high Lewis acidity, the capability to activate hydrogen and to effect the 1,1-carborations of terminal and internal alkynes under mild conditions.
November 15, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29136075/coordinatively-and-electronically-unsaturated-square-planar-cobalt-iii-complexes-of-a-pyridine-dianionic-pincer-ligand
#16
Faidh Hana, Alan J Lough, Gino G Lavoie
A series of low-valent Co(iii) square planar complexes supported by a dianionic pincer ligand bis(arylamido)pyridine ([NNN](2-)) was synthesized, including the first structurally characterized square planar hydroxide complex ([NNN]Co(OH), 4) of a 3d transition metal in the +3 oxidation state. The magnetic properties of the Co(iii) complexes were highly dependent on the charge of the complex and on the coordination environment of the metal. The diamagnetic cationic complex {[NNN]Co(py)}BF4 (2) can be converted to neutral paramagnetic complexes [NNN]Co(OR) (R = Ph 3a, iPr 3b, and H 4) by a simple substitution of the ancillary pyridine ligand in 2...
November 14, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29136074/crystal-structure-and-chemical-bonding-in-the-mixed-anion-compound-basf
#17
D Driss, S Cadars, P Deniard, J-Y Mevellec, B Corraze, E Janod, L Cario
BaSF was synthesised by a solid state reaction at high temperature and its crystal structure was determined thanks to X-ray diffraction on a single crystal. This transparent yellow fluorochalcogenide has an intergrowth structure built from the stacking of fluorite type layers and sulfur layers. In BaSF sulfur atoms form dimers with interatomic distances as short as 2.1074(10) Å. DFT calculations confirm that this compound is a band insulator with the Fermi level lying in between the antibonding π* and σ* molecular orbitals of the sulfur dimers...
November 14, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29136073/engineering-transition-metal-phosphide-nanomaterials-as-highly-active-electrocatalysts-for-water-splitting
#18
Yanmei Shi, Bin Zhang
Transition metal phosphide (TMP) nanomaterials are recently considered to be versatile electrocatalysts with excellent activity and stability towards water splitting. This Frontier article will highlight recent advances in engineering the composition and structure of TMPs for higher electrochemical performances.
November 14, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29136071/gold-nanoclusters-with-a-wide-range-of-fluorescence-characteristics-generated-in-situ-in-polymer-thin-films-potential-gas-sensing-application
#19
U Divya Madhuri, T P Radhakrishnan
Fabrication of gold nanoclusters (GNCs) with tunable fluorescence characteristics inside polymer thin films is attractive from the device application perspective. In this study, GNCs are generated in situ in poly(methyl methacrylate) films exploiting their weak reducing capability with no additional reducing agent, and by short and mild thermal annealing; the chemistry involved is probed through control experiments. The nanoclusters formed with ∼0.5 weight percent of gold are very stable and show appreciable fluorescence emission with a small Stokes shift (∼40 nm); interestingly, blending polystyrene enhances the fluorescence...
November 14, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/29134217/dicationic-phosphonium-salts-lewis-acid-initiators-for-the-mukaiyama-aldol-reaction
#20
Alejandro G Barrado, Julia M Bayne, Timothy C Johnstone, Christian W Lehmann, Douglas W Stephan, Manuel Alcarazo
Two strategies were used to prepare dicationic phosphonium cations. The first method consists of the reaction of 1-chlorocyclopropenium salts with phosphines to obtain cyclopropenium-substituted phosphonium salts 10a-f[BF4]. Anion exchange was performed to access the corresponding [B(C6F5)4](-) analogues 10a-f[B(C6F5)4], which showed much higher solubility in organic solvents. In addition, we developed a synthesis of dicationic phosphonium salts containing 2-, 3-, or 4-methylpyridinium substituents 11a-c[TfO], which were converted as well to their [B(C6F5)4](-) analogues 11a-c[B(C6F5)4]...
November 14, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
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