Chemo- and regioselective oxidation of substituted 2,3,4,9-tetrahydro-1H-carbazoles

Chemistry of Heterocyclic Compounds - Chemo- and regioselective oxidation of substituted 2,3,4,9-tetrahydro-1H-carbazoles was used to obtain 2,3,4,9-tetrahydro-1H-carbazol-1-ones or...     

Nonvolatile memory elements based on the intercalation of organic molecules inside carbon nanotubes

We propose a novel class of nonvolatile memory elements based on the modification of the transport properties of a conducting carbon nanotube by the presence of an encapsulated molecule. The guest molecule has two stable orientational positions relative to the nanotube that correspond to conducting and nonconducting states. The mechanism, governed by a local gating effect of the molecule on the electronic properties of the nanotube host, is studied using density functional theory. The mechanisms of reversible reading and writing of information are illustrated with a F4TCNQ molecule encapsulated inside a metallic carbon nanotube. Our results suggest that this new type of nonvolatile memory element is robust, fatigue-free, and can operate at room temperature.     

Highly dispersive large mode area photonic bandgap fiber

An all-silica photonic bandgap fiber composed of a low-index core surrounded by alternating high- and low-index rings allows us to achieve a large mode area (500 microm(2)) and large chromatic dispersion. Sharp resonances from the even Bragg mode to odd ring modes theoretically lead to 20,000 ps/(nm km) chromatic dispersion when large bends are applied. By nature, sharp resonances are sensitive to inhomogeneities along the fiber length. Under experimental conditions, the resonances are broadened and the dispersion coefficient is decreased to 1000 ps/(nm km). However, to the best of our knowledge, this is the largest dispersion coefficient reported using a large mode area fiber.     

Enantiopure Calcium Iminophosphonamide Complexes: Synthesis,Photoluminescence, and Catalysis

The synthesis of calcium complexes ligated by three different chiral iminophosphonamide ligands, L- H ( L =[Ph₂P{N(R)CH(CH₃)Ph}₂]), L′ -H ( L′ =[Ph₂P{NDipp}{N(R)CH(CH₃)Ph}]), (Dipp=2,6-ⁱPr₂C₆H₃), and L′′ -H ( L′′ =[Ph₂P{N(R)CH(CH₃)naph}₂]), (naph=naphthyl) is presented. The resulting structures [ L ₂Ca], [ L′ ₂Ca], and [ L′′ ₂Ca] represent the first examples of enantiopure homoleptic calcium complexes based on this type of ligands. The calcium complexes show blue–green photoluminescence (PL) in the solid state, which is especially bright at low temperatures. Whereas the emission of [ L′′ ₂Ca] is assigned to the fluorescence of naphthyl groups, the PL of [ L ₂Ca] and [ L′ ₂Ca] is contributed by long-lived phosphorescence and thermally activated delayed fluorescence (TADF), with a strong variation of the PL lifetimes over the temperature range of 5–295 K. Furthermore, an excellent catalytic activity was found for these complexes in hydroboration of ketones at room temperature, although no enantioselectivity was achieved.     

Crystal structure and thermal behavior of a chromium-piperazinium phosphate

(C₄N₂H₁₂)CrO(H_1.5PO₄)₂·H₂O has been synthesized hydrothermally using piperazine as organic template. Its crystal structure was solved ab initio using synchrotron powder X-ray diffraction data [monoclinic, a = 16.9649(4) Å, b = 9.8609(2) Å, c = 7.14375(14) Å, and β = 94.896(3)°, space group P2₁/a, Z = 4]. 1D structure is composed by isolated infinite anionic chains [CrO(H_1.5PO₄)₂]_n (vertex-sharing {CrO₆} octahedra joined by phosphate moieties). Their 2D plate-like morphology is propitiated by a very strong inter-chain interaction (P–O···H···O–P symmetric hydrogen bonds). KAS isoconversional method was applied to determine the activation energy for both thermal and thermo-oxidative decomposition of (C₄N₂H₁₂)CrO(H_1.5PO₄)₂·H₂O.     

Photolysis of 3-(1-acyl-5-aryl-3-pyrazolinyl)coumarins—Effective Fluorescence Decay

Photophysical characteristics of new 3-(1-acyl-5-aryl-3-pyrazolinyl)coumarins have been measured. These coumarin derivatives are found to be effective fluorophores and show high values of quantum yields of fluorescence both in nonpolar and in polar solvents. The 3-(1-acyl-5-aryl-3-pyrazolinyl)coumarins turned to be photosensitive compounds and undergo photolysis under irradiation in the range of 310–465 nm. Photolysis is suggested to include retro-cyclization and retro-condensation steps. The process is accompanied by a sharp drop of fluorescence that can be of interest for the creation of new media in optical recording of information.     

Kinetics of D,L–Lactide Polymerization Initiated with Zirconium Acetylacetonate

The kinetic of D,L-lactide polymerization in presence of biocompatible zirconium acetylacetonate initiator was studied by differential scanning calorimetry in isothermal mode at various temperatures and initiator concentrations. The enthalpy of D,L-lactide polymerization measured directly in DSC cell was found to be ΔH=−17.8±1.4 kJ mol⁻¹. Kinetic curves of D,L-lactide polymerization and propagation rate constants were determined for polymerization with zirconium acetylacetonate at concentrations of 250–1000 ppm and temperature of 160–220 °C. Using model or reversible polymerization the following kinetic and thermodynamic parameters were calculated: activation energy E_a=44.51±5.35 kJ mol⁻¹, preexponential constant lnA=15.47±1.38, entropy of polymerization ΔS=−25.14 J mol⁻¹ K⁻¹. The effect of reaction conditions on the molecular weight of poly(D,L-lactide) was shown.     

Orthogonal Cationic and Radical RAFT Polymerizations to Prepare Bottlebrush Polymers

An orthogonal combination of cationic and radical RAFT polymerizations is used to synthesize bottlebrush polymers using two distinct RAFT agents. Selective consumption of the first RAFT agent is used to control the cationic RAFT polymerization of a vinyl ether monomer bearing a secondary dormant RAFT agent, which subsequently allows side‐chain polymers to be grafted from the pendant RAFT agent by a radical‐mediated RAFT polymerization of a different monomer, thus completing the synthesis of bottlebrush polymers. The high efficiency and selectivity of the cationic and radical RAFT polymerizations allow both polymerizations to be conducted in one‐pot tandem without intermediate purification.     

Atroposelective Synthesis of Axially Chiral N‐Arylpyrroles by Chiral‐at‐Rhodium Catalysis

A transformation of fluxional into configurationally stable axially chiral N‐arylpyrroles was achieved with a highly atroposelective electrophilic aromatic substitution catalyzed by a chiral‐at‐metal rhodium Lewis acid. Specifically, N‐arylpyrroles were alkylated with N‐acryloyl‐1H‐pyrazole electrophiles in up to 93 % yield and with up to >99.5 % ee, and follow‐up conversions reveal the synthetic utility of this new method. DFT calculations elucidate the origins of the observed excellent atroposelectivity.