Supramolecular Assembly of Interfacial Nanoporous Networks with Simultaneous Expression of Metal–Organic and Organic‐Bonding Motifs

The formation of 2D surface‐confined supramolecular porous networks is scientifically and technologically appealing, notably for hosting guest species and confinement phenomena. In this study, we report a scanning tunneling microscopy (STM) study of the self‐assembly of a tripod molecule specifically equipped with pyridyl functional groups to steer a simultaneous expression of lateral pyridyl–pyridyl interactions and Cu–pyridyl coordination bonds. The assembly protocols yield a new class of porous open assemblies, the formation of which is driven by multiple interactions. The tripod forms a purely porous organic network on Ag(111), phase α, in which the presence of the pyridyl groups is crucial for porosity, as confirmed by molecular dynamics and Monte Carlo simulations. Additional deposition of Cu dramatically alters this scenario. For submonolayer coverage, three different porous phases coexist (i.e., β, γ, and δ). Phases β and γ are chiral and exhibit a simultaneous expression of lateral pyridyl–pyridyl interactions and twofold Cu–pyridyl linkages, whereas phase δ is just stabilized by twofold Cu–pyridyl bonds. An increase in the lateral molecular coverage results in a rise in molecular pressure, which leads to the formation of a new porous phase (ε), only coexisting with phase α and stabilized by a simultaneous expression of lateral pyridyl–pyridyl interactions and threefold Cu–pyridyl bonds. Our results will open new avenues to create complex porous networks on surfaces by exploiting components specifically designed for molecular recognition through multiple interactions.     

Sensitive Anodic Stripping Voltammetric Copper Ions Determination Performed in Double Deposition and Double Stripping Steps System for Real Water Samples Analysis

The article reports on utilization of double deposition and stripping steps for increasing sensitivity of Cu(II) determination by anodic stripping voltammetry (ASV) at two lead film working electrodes. A significant preconcentration of copper was achieved thanks to utilization of a simple design of four electrodes system that gives possibility to perform one measurement cycle consisting of two deposition and two stripping steps. Due to the fact that deposition step is doubled, the concentration of Pb(II) needed to lead film electrodes formation was significantly reduced as compared to traditional procedures using three electrodes system. The analytical procedure of Cu(II) determination was optimized. The experimental factors: supporting electrolyte's pH and its concentration, lead ions concentration, potential and time of deposition at both working electrodes were studied. The Cu(II) peak current was linearly dependent on its concentration from 5×10^?10 to 2×10^?8 mol L^?1 (deposition time of 270 and 160 s at the first and the second working electrode, respectively). The obtained detection limit for copper ions determination was 2.1×10^?10 mol L^?1. The described procedure was validated by analysis of two water certified reference materials. The described procedure was also utilized for real water sample analysis.     

Unexpected Vulnerability of DPEphos to C−O Activation in the Presence of Nucleophilic Metal Hydrides

C−O bond activation of DPEphos occurs upon mild heating in the presence of [Ru(NHC)₂(PPh₃)₂H₂] (NHC=N-heterocyclic carbene) to form phosphinophenolate products. When NHC=IEt₂Me₂, C−O activation is accompanied by C−N activation of an NHC ligand to yield a coordinated N-phosphino-functionalised carbene. DFT calculations define a nucleophilic mechanism in which a hydride ligand attacks the aryl carbon of the DPEphos C−O bond. This is promoted by the strongly donating NHC ligands which render a trans dihydride intermediate featuring highly nucleophilic hydride ligands accessible. C−O bond activation also occurs upon heating cis-[Ru(DPEphos)₂H₂]. DFT calculations suggest this reaction is promoted by the steric encumbrance associated with two bulky DPEphos ligands. Our observations that facile degradation of the DPEphos ligand via C−O bond activation is possible under relatively mild reaction conditions has potential ramifications for the use of this ligand in high-temperature catalysis.     

Heteroaromatic Belts through Fold‐in Synthesis: Mechanistic Insights into a Macrocycle‐Templated Friedel–Crafts Alkylation

Direct alkylation of 9,9′,9′′‐triethyl[2.2.2](2,7)carbazolophane with dimethoxymethane or paraformaldehyde affords a belt‐like heteroaromatic structure, which forms as a kinetic product in acid‐catalyzed condensations. In a competing, thermodynamically favored process, polymeric structures are formed by a largely regioselective condensation of stereochemically rigid “semi‐belts”. The relationship between these reactivity routes is rationalized in terms of strain release and differential reversibility of consecutive condensation steps.     

Accelerating Diffusion‐Ordered NMR Spectroscopy by Joint Sparse Sampling of Diffusion and Time Dimensions

Diffusion‐ordered multidimensional NMR spectroscopy is a valuable technique for the analysis of complex chemical mixtures. However, this method is very time‐consuming because of the costly sampling of a multidimensional signal. Various sparse sampling techniques have been proposed to accelerate such measurements, but they have always been limited to frequency dimensions of NMR spectra. It is now revealed how sparse sampling can be extended to diffusion dimensions.     

Thick-film graphite electrodes in stripping voltammetry

Various types of modified thick-film graphite electrodes are reviewed. Two modification options are available: either in situ modified or beforehand. Electrodes modified in situ by various organic compounds were used for the determination of W, Mo, Cr, Ni and Mn by adsorptive stripping voltammetry. Insoluble inorganic salts, insoluble organic complexes or soluble compounds protected with Nafion were used for modification of the electrode surface beforehand. These pre-conditioned electrodes permit quantification of Pb, Cd, Cu, Zn, Sn, As and Hg ions. The detection limits of these elements were in the sub-μg/L range. The relative standard deviation did not exceed 10–15%. Measurements were made without deaeration of test solutions and normally without destroying small organic matter found in surface waters. A number of characteristics, such as the formation of well-shaped peaks and stable increments of peaks after standard additions, as well as elimination of the mechanical surface regeneration stage and metallic mercury or its soluble salts from the analytical procedure and a long shelf-life of the electrodes make them promising for electroanalysis and for application in portable field instruments. Received: 16 November 1998 / Revised: 16 February 1999 / Accepted: 20 February 1999     

Spectroscopy and Photophysics of Monomethyl-Substituted Derivatives of 5-Deazaalloxazine and 10-Ethyl-5-Deaza-Isoalloxazine

Steady-state and time-resolved spectra were used to describe the singlet and triplet states of 8-methyl-5-deazaalloxazine (8-Me-5-DAll), 9-methyl-5-deazaalloxazine (9-Me-5-DAll) and 10-ethyl-5-deaza-isoalloxazine (10-Et-5-DIAll). Solvatochromic properties were described using different polarity scales, including Δf and the four-parameter scale proposed by Catalán. The results indicate that the Catalán scale shows a strong influence of solvent acidity (hydrogen-bond donating ability) on the emission properties of 8-Me-5-DAll and 9-Me-5-DAll. These results indicate the importance of intermolecular solute-solvent hydrogen-bonding interactions in the excited state of these compounds. Contrary to deazaalloxazines, solvent acidity affects the absorption spectra of 10-Et-5-DIAll. Fluorescence lifetimes and quantum yields and also transient absorption spectra were determined for all of the compounds studied. Electronic structure and S ₀ -S _i , S ₀ -T _i , T ₁ -T _i transitions energies and oscillator strengths were calculated using the TD-DFT methods. Theoretical calculations were compared to experimental data.     

Thermal Stability and Flammability of Polypropylene-Silsesquioxane Nanocomposites

This article presents a study of the thermal stability of polypropylene-based nanocomposites filled with tetrasilanolphenyl silsesquioxane (phPOSS). Nanofillers were introduced into a polypropylene matrix in three different amounts: 2, 5, and 10 wt.%. Investigations were carried out by means of thermogravimetric analyses conducted in inert and oxidizing atmospheres, Fourier transform-infrared spectroscopy, scanning electron microscopy, and flammability UL-94 test. The addition of phPOSS into the polymeric matrix increased thermal stability in comparison to neat iPP and introduced significant changes in the flammability of iPP/phPOSS nanocomposites.