Microwave‐Assisted Synthesis and Transformations of Cationic CpRu(II)(naphthalene) and CpRu(II)(naphthoquinone) Complexes

Details of the direct synthesis of cationic Ru(II)(η⁵‐Cp)(η⁶‐arene) complexes from ruthenocene using microwave heating are reported. Developed for the important catalyst precursor [Ru(II)(η⁵‐Cp)(η⁶‐1‐4,4a,8a‐naphthalene)][PF₆] reaction time could be shortened from three days to 15 min. The method was extended to [Ru(II)(η⁶‐benzene)(η⁵‐Cp)][PF₆], [Ru(II)(η⁵‐Cp)(η⁶‐toluene)][PF₆], [Ru(II)(η⁵‐Cp)(η⁶‐mesitylene)][PF₆], [Ru(II)(η⁵‐Cp)(η⁶‐hexamethylbenzene)][PF₆], [Ru(II)(η⁵Cp)(η⁶‐indane)][PF₆], [Ru(II)(η⁵‐Cp)(η⁶‐2,6‐dimethylnaphthalene)][PF₆], and [Ru(II)(η⁵‐Cp)(η⁶‐pyrene)][PF₆]. 1‐methylnaphthalene and 2,3‐dimethylnaphthalene afforded mixtures of regioisomeric complexes. [Ru(Cp)(CH₃CN)₃][PF₆], derived from the naphthalene precursor provided access to the cationic RuCp complexes of naphthoquinone, tetralindione, 1,4‐dihydroxynaphthalene, and 1,4‐dimethoxynaphthalene. Reduction of the tetralindione complex afforded selectively the endo,endo diol derivative. X‐Ray structures of five complexes are reported.     

3,4‐Bis[(4‐methoxy­benzo­yl)methyl­sulfanyl]thio­phene

A new type of thio­phene derivative having α‐thio­ketone groups at the 3‐ and 4‐positions, viz. the title compound, C₂₂H₂₀O₄S₃, has been prepared and studied by NMR spectroscopy and single‐crystal X‐ray diffraction techniques. The mol­ecule is nearly planar, the dihedral angles between the essentially planar thio­phene and benzene rings being 9.4 (1) and 10.6 (1)°. One of the thio­ketone O atoms is involved in an inter­molecular C—H⋯O hydrogen‐bonding inter­action.     

Structures and Energetics of NI3 and N2I4

We have applied new methods for performing coupled-cluster calculations to small molecules containing iodine atoms; specifically, NI₃ and N₂I₄. Because NI₃ is known to be very reactive, attempts to measure its thermodynamic properties have been challenging at best. To date, N₂I₄ has not been isolated, and our results suggest that its isolation will be just as challenging. We find that the ΔH_f(NI₃)=+307.7 kJ mol⁻¹ and ΔH_f(N₂I₄)=+551.6 kJ mol⁻¹, confirming that they are unstable with respect to their decomposition products N₂ and I₂.     

The Crystallography of Interphase Boundaries Between Silicon Carbide and Silicon Nitride in Silicon Nitride—Silicon Carbide Particulate Composites

Interphase boundaries between 3C SiC grains and two different -Si₃N₄ morphologies in Si₃N₄–SiC composites have been studied by transmission electron microscopy. In general, boundaries between small -Si₃N₄ intragranular precipitates and surrounding SiC grains were relatively free of intergranular films, whereas boundaries between large -Si₃N₄ grains and adjacent SiC grains were invariably covered with thin intergranular films. Orientation relationships approximating to [110] 3C SiC [0001] -Si₃N₄ and (001) 3C SiC (10 0) -Si₃N₄ were found to dominate between 3C SiC grains and the intragranular -Si₃N₄ precipitates, but there was no evidence of any favoured orientation relationship between the large -Si₃N₄ grains and adjacent SiC grains. The rationale for special orientation relationships arising when there is no intergranular film present at 3C SiC–-Si₃N₄ interfaces is explored geometrically using the near-coincidence site lattice model, with the significant result that the dominant orientation relationships between 3C SiC grains and the intragranular -Si₃N₄ precipitates have low misfits relative to all other possible orientation relationships between 3C SiC and -Si₃N₄.     

On the origin of the 2.2-2.3 eV photoluminescence from chemically etched germanium

The photoluminescence (PL) at ∼2.2-2.3 eV from Ge-based nanocrystalline materials is described in the literature as nanocrystal size-independent. We have observed visible luminescence from two different types of stain-etched Ge samples, one prepared after Sendova-Vassileva et al. (Thin Solid Films 255 (1995) 282) in a solution of H₂O₂:HF at 50:1 volume ratio, and the other in a solution of HF:H₃PO₄:H₂O₂ at 34:17:1 volume ratio. Energy dispersive X-ray analysis (EDX), Raman and FTIR spectroscopy, and the near edge X-ray absorption structure (XANES), indicate that the chemically etched Ge layers of the former type of samples are composed of non-stoichometric Ge oxides, i.e. GeO_x (0<x<2), and free from any Ge nanoconstructions. It is also suggested from XANES that the latter type of chemically etched Ge samples comprise 8-9 nm nanocrystals of Ge, surface-covered with mainly oxygen. Photoluminescence occurred at ∼2.3 eV for all samples. The PL behavior of the latter type of chemically etched Ge on annealing in different chemical environments (air or H) allowed us to conclude that the PL from these materials, as well as that from those Ge-based nanocrystalline materials reported in the literature, is from GeO_xs.     

Intramolecular interactions in ethyl bis-(2,4-dinitrophenyl)acetate

The crystal structure of ethyl bis(2,4-dinitrophenyl)acetate, determined by room temperature X-ray diffraction, shows that this crowded molecule contains two short intramolecular interactions between nitro oxygen atoms and electron deficient carbon atoms. One mimics an early stage of the nucleophilic addition to a carbonyl group (O...C, 2.730 Å), and the other mimics an early stage of a Michael reaction (O...C, 2.854 Å). Crystal data: C₁₆H₁₂N₄O₁₀, M _r = 420.29, a = 10.079(1), b = 11.139(1), c = 16.162(1) Å, = 91.319(7)°, monoclinic, P2₁/c, Z = 4.     

Novel two-band ratiometric fluorescence probes with different location and orientation in phospholipid membranes

3-hydroxyflavone (3-HF) derivatives are very attractive fluorescence sensors due to their ability to respond to small changes in their microenvironment via a dramatic alteration of the relative intensities of their two well-separated emission bands. We developed fluorescence probes with locations at different depths and orientations of 3-HF moiety in the phospholipid bilayer, which determine their fluorescence behavior. While the spectral shifts of the probes correlate with their binding site polarity, the intensity ratio is a complex parameter that is also sensitive to the local hydration. We demonstrate that even the deeply located probes sense this hydration effect, which can be modulated by the charge of the lipid heads and is anisotropic with respect to the bilayer plane. Thus the two-band ratiometric fluorescence probes can provide multiparametric information on the properties of lipid membranes at different depths.     

Synthesis,Structure, DFT Calculations,and In Silico Toxic Potential of Ni(II), Zn(II), and Fe(II) Complexes with a Tridentate Schiff Base

Russian Journal of General Chemistry - The Schiff base ligand has been synthesized from 5-bromo-2-hydroxybenzaldehyde and ethyl...     

2-D analysis of Ge implanted SiO2 surfaces by laser-induced breakdown spectroscopy

2-D elemental distribution of Ge in silicon oxide substrates with differing implantation doses of between 3 × 10¹⁶ cm^− 2 and 1.5 × 10¹⁷ cm^− 2 has been investigated by Laser-Induced Breakdown Spectroscopy (LIBS). Spectral emission intensity has been optimized with respect to time, crater size, ablation depth and laser energy. Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) coupled with Energy-Dispersive X-Ray Spectroscopy (EDX) have been utilized to obtain crater depth, morphology and elemental composition of the sample material, respectively. LIBS spectral data revealed the possibility of performing 2-D distribution analysis of Ge atoms in silicon oxide substrate. EDX analysis results confirmed that LIBS is capable to detect Ge atoms at concentrations lower than 0.2% (atomic). LIBS as a fast semi-quantitative analysis method with 50 µm lateral and 800 nm depth resolution has been evaluated. Results illustrate the potential use of LIBS for rapid, on-line assessment of the quality of advanced technology materials during the manufacturing process.     

Reversible Doping of a Dithienothiophene‐Based Conjugated Microporous Polymer

Dithienothiophene (DTT) based conjugated microporous polymers (CMPs) were synthesized by bulk and electrochemical oxidative polymerizations. Spectroelectrochemical measurements showed that DTT‐CMP can be reversibly oxidized and reduced, accompanied by a significant change of the absorption properties making the material interesting for electrochromic devices. Reversible doping and dedoping of the bulk polymer network was also observed using iodine and ammonia, respectively. Nitrogen gas sorption measurements of the neutral, doped, and dedoped polymer networks indicated the presence of iodide species within the pores, and the conductivity of the networks is highly increased upon doping with iodine. The introduction of the strong electron donor DTT into a conjugated porous network, and the ability for redox switching, make DTT‐CMPs interesting materials for organo(opto)electronic devices and sensors.