On the Aqueous Chemistry of the UIV–DOTA Complex

The 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) aqueous complex of U^IV with H₂O, OH⁻, and F⁻ as axial ligands was studied by using UV/Vis spectrophotometry, ESI-MS, NMR spectroscopy, X-ray crystallography, and electrochemistry. The U^IV–DOTA complex with either water or fluoride as axial ligands was found to be inert to oxidation by molecular oxygen, whereas the complex with hydroxide as an axial ligand slowly hydrolyzed and was oxidized by dioxygen to a diuranate precipitate. The combined data set acquired shows that, although axial substitution of fluoride and hydroxide ligands instead of water does not seem to significantly change the aqueous DOTA complex structure, it has an important effect on the electronic configuration of the complex. The U^IV/U^III redox couple was found to be quasi-reversible for the complex with both axially bonded H₂O and hydroxide, but irreversible for the complex with axially bonded fluoride. Intriguingly, binding of the axial fluoride renders the irreversible one-electron U^V/U^IV oxidation of the [U^IV(DOTA)(H₂O)] complex quasi-reversible, which suggests the formation of the short-lived pentavalent form of the complex, an aqueous non-uranyl chelated U^V cation.     

Certain features of graphite oxide functional groups as drawn from simulations and experiment

General experimental information retrieved from X-ray photoelectron and infrared spectra of synthesized graphite oxide (GO) specimens combined with the results of nonempirical quantum chemical simulations of model GO fragments carried out at the density functional level with the use of B3LYP hybrid exchange-correlation functional and extended 6-31G(d,p) Gaussian basis set provided an insight in the possible surface functionalization of graphite sheets upon oxidation with an emphasis on epoxide and hydroxide groups. IR spectral fingerprints of hydroxide and epoxide groups were found in certain frequency ranges that regularly shift depending on particular local neighborhoods of the groups on a GO surface. A noticeable role of hydrating water molecules was discovered.

     

A Trigonal Prismatic Cobalt(II) Complex as a Single Molecule Magnet with a Reduced Contribution from Quantum Tunneling

Herein, we report a new trigonal prismatic cobalt(II) complex that behaves as a single molecule magnet. The obtained zero-field splitting, which is also directly accessed by THz-EPR spectroscopy (−102.5 cm⁻¹), results in a large magnetization reversal barrier U of 205 cm⁻¹. Its effective value, however, is much lower (101 cm⁻¹), even though there is practically no contribution from quantum tunneling to magnetization relaxation.     

High pressure synthesis and transport properties of a perfluorinated sulfocationic exchange membrane

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Bimetallic nanowire sensors for extracellular electrochemical hydrogen peroxide detection in HL-1 cell culture

Journal of Solid State Electrochemistry - The present study of nanoelectrochemical sensors prepared by directed electrochemical nanowire assembly (DENA) is defined by the requirements of...     

Obituary - Boris Yakovlevich Kaplan

Journal of Solid State Electrochemistry -     

Highly Stereocontrolled Ring‐Opening Polymerization of Racemic Alkyl β‐Malolactonates Mediated by Yttrium [Amino‐alkoxy‐bis(phenolate)] Complexes

Yttrium [amino‐alkoxy‐bis(phenolate)]amido complexes have been used for the ring‐opening polymerization (ROP) of racemic alkyl β‐malolactonates (4‐alkoxycarbonyl‐2‐oxetanones, rac‐MLA^Rs) bearing an allyl (All), benzyl (Bz) or methyl (Me) lateral ester function. The nature of the ortho‐substituent on the phenolate rings in the metal ancillary dictated the stereocontrol of the ROP, and consequently the syndiotactic enrichment of the resulting polyesters. ROP promoted by catalysts with halogen (Cl, Br)‐disubstituted ligands allowed the first reported synthesis of highly syndiotactic PMLA^Rs (P_r ≥ 0.95); conversely, catalysts bearing bulky alkyl and aryl ortho‐substituted ligands proved largely ineffective. All polymers have been characterized by ¹H and ¹³C{¹H} NMR spectroscopy, MALDI‐ToF mass spectrometry and DSC analyses. Statistical and thermal analyses enabled the rationalization of the chain‐end control mechanism. Whereas the stereocontrol of the polymerization obeyed a Markov first‐order (Mk1) model for the ROP of rac‐MLA^Bz and rac‐MLA^All, the ROP of rac‐MLA^Me led to a chain end‐control of Markov second‐order type (Mk2). DFT computations suggest that the high stereocontrol ability featured by catalysts bearing Cl‐ and Br‐substituted ligands does not likely originate from halogen bonding between the halogen substituent and the growing polyester chain.