Electron paramagnetic resonance and electron nuclear double resonance of NaCl:Rh2+: A comparison between similarly doped Bridgman- and solution-grown single crystals

In a recent electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) study several new rhodium related centres in a Bridgman-grown crystal were reported. For two centres a detailed microscopic model was established. The primary Rh²⁺ centre was identified as a [RhCl₆]^4? complex with a single charge compensating Na⁺ vacancy in a next nearest neighbour position. A second centre was identified as a rhodium dimer. Two other Rh²⁺ centres, with apparent axial symmetry, remained unidentified. In the present study a detailed comparison between Rh²⁺ defects in Bridgman- and solution-grown NaCl crystals is presented. One of the previously unidentified Rh²⁺ centres is shown not to be axial but to have orthorhombic-I symmetry and is identified as a cis-[RhCl₆]^4? complex with two next nearest neighbour Na⁺ vacancies. For the primary centre additional ENDOR interactions confirm the model mentioned above. Finally a comparison is made between the temperature stability of the primary and orthorhombic-I centre in Bridgman-grown and similarly doped solution-grown NaCl crystals.     

Identification of primary free radicals in trehalose dihydrate single crystals X-irradiated at 10 K

Primary free radical formation in trehalose dihydrate single crystals X-irradiated at 10 K was investigated at the same temperature using X-band Electron Paramagnetic Resonance (EPR), Electron Nuclear Double Resonance (ENDOR) and ENDOR-induced EPR (EIE) techniques. The ENDOR results allowed the unambiguous determination of six proton hyperfine coupling (HFC) tensors. Using the EIE technique, these HF interactions were assigned to three different radicals, labeled R1, R2 and R3. The anisotropy of the EPR and EIE spectra indicated that R1 and R2 are alkyl radicals (i.e. carbon-centered) and R3 is an alkoxy radical (i.e. oxygen-centered). The EPR data also revealed the presence of an additional alkoxy radical species, labeled R4. Molecular modeling using periodic Density Functional Theory (DFT) calculations for simulating experimental data suggests that R1 and R2 are the hydrogen-abstracted alkyl species centered at C5' and C5, respectively, while the alkoxy radicals R3 and R4 have the unpaired electron localized mainly at O2 and O4'. Interestingly, the DFT study on R4 demonstrates that the trapping of a transferred proton can significantly influence the conformation of a deprotonated cation. Comparison of these results with those obtained from sucrose single crystals X-irradiated at 10 K indicates that the carbon situated next to the ring oxygen and connected to the CH(2)OH hydroxymethyl group is a better radical trapping site than other positions.     

Light-induced excited spin state trapping and charge transfer in trigonal bipyramidal cyanide-bridged complexes

Three members of the family of trigonal bipyramidal (TBP) complexes of general formula [M(tmphen)(2)](3)[M'(CN)(6)](2) (tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline) or [M(3)M'(2)], which are known to exhibit thermally induced spin crossover and charge transfer, have been investigated for optical and photomagnetic properties. The light-induced excited spin-state trapping (LIESST) effect found in classical spin crossover compounds, such as [Fe(phen)(2)(NCS)(2)], was explored for the [Fe(3)Fe(2)] and [Fe(3)Co(2)] compounds. Similarly, inspired by the light-induced charge-transfer properties of K(0.2)Co(1.4)[Fe(CN)(6)]·6.9H(2)O and related Prussian blue materials, the possibility of photo-induced magnetic changes was investigated for the [Co(3)Fe(2)] TBP complex. Optical reflectivity and magnetic susceptibility measurements were used to evaluate the photoactivity of these compounds. A comparison of these data before and after light irradiation demonstrates that (i) the spin crossover of the Fe(II) centers in the [Fe(3)Fe(2)] and [Fe(3)Co(2)] analogues and the (ii) charge transfer events in the [Co(3)Fe(2)] complex occur with temperature and irradiation. In addition, photomagnetic behavior is exhibited by all three compounds. The photo-conversion efficiency has been estimated at 20% of photo-induced high spin Fe(II) centers in [Fe(3)Co(2)], 30% of paramagnetic Co(II)-Fe(III) pairs in [Co(3)Fe(2)], and less than 2% of photo-induced high spin Fe(II) centers in [Fe(3)Fe(2)].     

Gas Phase Reactions of 1,3,5-Triazine: Proton Transfer,Hydride Transfer,and Anionic σ-Adduct Formation

The gas phase reactivity of 1,3,5-triazine with several oxyanions and carbanions, as well as amide, was evaluated using a flowing afterglow-selected ion flow tube mass spectrometer. Isotopic labeling, H/D exchange, and collision induced dissociation experiments were conducted to facilitate the interpretation of structures and fragmentation processes. A multi-step (→ HCN + HC₂N₂⁻ → CN⁻ + 2 HCN) and/or single-step (→ CN⁻ + 2 HCN) ring-opening collision-induced fragmentation process appears to exist for 1,3,5-triazinide. In addition to proton and hydride transfer reactions, the data indicate a competitive nucleophilic aromatic addition pathway (S_NAr) over a wide range of relative gas phase acidities to form strong anionic σ-adducts (Meisenheimer complexes). The significant hydride acceptor properties and stability of the anionic σ-adducts are rationalized by extremely electrophilic carbon centers and symmetric charge delocalization at the electron-withdrawing nitrogen positions. The types of anion-arene binding motifs and their influence on reaction pathways are discussed.     

Long-range alignment of gold nanorods in electrospun polymer nano/microfibers

In this study, a scalable fabrication technique for controlling and maintaining the nanoscale orientation of gold nanorods (GNRs) with long-range macroscale order has been achieved through electrospinning. The volume fraction of GNRs with an average aspect ratio of 3.1 is varied from 0.006 to 0.045 in aqueous poly(ethylene oxide) solutions to generate electrospun fibers possessing different GNR concentrations and measuring 40-3000 nm in diameter. The GNRs within these fibers exhibit excellent alignment with their longitudinal axis parallel to the fiber axis n. According to microscopy analysis, the average deviant angle between the GNR axis and n increases modestly from 3.8 to 13.3° as the fiber diameter increases. Complementary electron diffraction measurements confirm preferred orientation of the {100} GNR planes. Optical absorbance spectroscopy measurements reveal that the longitudinal surface plasmon resonance bands of the aligned GNRs depend on the polarization angle and that maximum extinction occurs when the polarization is parallel to n.     

On the Image of the Totaling Functor

Let A be a differential graded (DG) algebra with a trivial differential over a commutative unital ring. This paper investigates the image of the totaling functor, defined from the category of complexes of graded A-modules to the category of DG A-modules. Specifically, we exhibit a special class of semifree DG A-modules which can always be expressed as the totaling of some complex of graded free A-modules. As a corollary, we also provide results concerning the image of the totaling functor when A is a polynomial ring over a field.     

Krull dimension for differential graded algebras

We introduce a naive notion of a system of parameters for a homologically finite complex over a commutative noetherian local ring and compare it to the system of parameters defined by Christensen. We show that these notions differ in general but that they agree when the complex in question is a DG R-algebra. In this case we also show that the Krull dimension defined in terms of the lengths of such systems of parameters agrees with Krull dimensions defined in terms of certain chains of prime ideals.     

Electron paramagnetic resonance study of S− and S− 3

Abstract

Two new sulphur are reported in monocristalline rubidiumchloride doped with rubidium and sulphur, and irradiated with X-rays at room temperature. By an extensive comparison with other experimental data on chalcogen centres in alkali halides an interstitial RbCl:S^? and a substitutional RbCl:S^? ₃ model is proposed for these paramagnetic defects. Theoretical calculations confirm the S^? ion model for the former.     

Interfacial ketene via the photo‐Wolff rearrangement for the modification of monolayer protected gold nanoparticles

An interfacial diazoketone‐modified gold nanoparticle (AuNP) was prepared and characterized by ¹H NMR and IR spectroscopy, TGA and TEM. Irradiation of the diazoketone leads to loss of nitrogen and the formation an interfacial ketene–AuNP via the photo‐Wolff rearrangement, evidenced by the loss of the characteristic C = N = N signal at 2068 cm^?1 in the IR spectrum and the growth of a new signal at 2100 cm^?1 indicative of the ketene. This ketene is relatively stable in the absence of added nucleophiles, but reacts quickly with oxygen nucleophiles illustrating the potential use of this ketene–AuNP as a template for a wide range of surface modifications. Copyright © 2013 John Wiley & Sons, Ltd.