Search results for "cationic polymerization"
showing 10 items of 441 documents
The Szilard–Chalmers effect in macrocyclic ligands to increase the specific activity of reactor-produced radiolanthanides: Experiments and explanatio…
2012
Abstract Successful utilization of medical isotopes in the radiolabeling reactions to a significant degree depends on the technically achievable specific activity. In this respect, the Szilard-Chalmers effect is considered in detail as a radiochemical tool to increase the specific activity of radionuclides produced by direct nuclear reactions. In the present study, a physico-chemical model is described utilizing the specific aspects of thermodynamically and kinetically stabilised metal-ligand complexes. The approach is applied as a proofof- principle study to increase the specific activity of 166Ho, produced via the (n, γ) nuclear reaction. As a target material, 165Ho-DOTA is used. In this …
Pulse radiolysis and theoretical investigation on the initial mechanism of the e-beam polymerization of epoxy resins. The results obtained on (phenox…
2007
Abstract The radical cation of (phenoxymethyl)oxirane ( PGE ⋅ + ) is generated by pulse radiolysis in dichloromethane solution and by direct action of radiation on the title compound. In the pure system its UV–vis spectrum is characterized by two bands at 340 and 430 nm, such that the electronic structure corresponds to a dipole bearing the positive charge on the phenoxy side. At the same time, the phenoxy-oxirane bridge is weakened. Then, the radical cation fragments into a phenoxonium ion and an oxyranylmethyl radical ( k PGE - fragm = 1.16 × 10 7 s - 1 ) . The latter immediately rearranges to an allyloxyl radical by ring opening. It is then conceived that the action of onium salts, as ra…
Room temperature ionic liquids structure and its effect on the mononuclear rearrangement of heterocycles: an approach using thermodynamic parameters.
2006
The kinetics of the rearrangement of the Z-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole (1) into the relevant 4-benzoylamino-2,5-diphenyl-1,2,3-triazole (2) induced by amines have been studied in five room-temperature ionic liquids (RTILs) at different temperatures. The kinetic data collected show that both cationic and anionic parts of RTILs significantly influence the reactivity of the title reaction. The calculated activation parameters allow us to advance hypotheses about the weak interactions operating in RTIL solutions.
Oxidative C-N fusion of pyridinyl-substituted porphyrins.
2018
International audience; The mild (electro) chemical oxidation of pyridin-2-ylthio-meso substituted Ni(II) porphyrins affords C-N fused cationic and dicationic pyridinium-based derivatives. These porphyrins are fully characterized and the molecular structure of one of them was confirmed by X-ray crystallography. A mechanism for the intramolecular oxidative C-N coupling is proposed based on theoretical calculations and cyclic voltammetry analyses.
Quantitative structure-retention relationships for ionic and non-ionic compounds in biopartitioning micellar chromatography
2004
Quantitative structure–retention relationships, QSRRs, represent a powerful tool in chromatography. The objectives of QSRR studies are to predict the chromatographic retention behaviour of solutes based on their structural properties, to elucidate retention mechanisms, to optimize the separation of complex mixtures or to prepare experimental designs. In this paper, using the retention factors of 151 structurally unrelated solutes that cover a wide range of hydrophobicity, molecular size, hydrogen bonding properties and ionization degrees obtained in biopartitioning micellar chromatography (BMC) at different Brij35 micellar concentrations, several multivariate QSRR models are tested. It is d…
Efficient orange light-emitting electrochemical cells
2012
We report the first bis-cyclometalated cationic iridium(III) complex with N-aryl-substituted 1H-imidazo [4,5-f][1,10]phenanthroline. The complex emits yellow-orange phosphorescence with a maximum at 583 nm, a quantum yield of 43%, and an excited-state lifetime of 910 ns in argon-saturated dichloromethane. Optimized orange light-emitting electrochemical cells with the new Ir(III) complex exhibit fast turn-on, a peak luminance of 684 cd m(-2) and a peak efficacy of 6.5 cd A(-1); in 850 h of continuous operation their luminance and efficacy decrease only by 20%.
Phosphorylated micro- vs. nano-cellulose: a comparative study on their surface functionalisation, growth of titanium-oxo-phosphate clusters and remov…
2019
Controlled cellulose disassembly affords many variants including amorphous micro-sized cellulose crystals (MCC) and cellulose nano-sized crystals (CNC), which have emerged recently as green and sustainable nanomaterials. Unfortunately, their lower reactivity and thermal and chemical instability constitute an impediment for multifaceted nanoscience and nanotechnology usage. Herein, MCC and CNC are functionalised using two phosphorus derivatives (phosphoryl chloride and hexachlorocyclotriphosphazene), under acid-free, urea-free and corrosive-free, gentle experimental conditions. Notably, CNC can accommodate more phosphorus species compared to MCC, with the bulky phosphazene precursor being le…
Wide-Bite-Angle Diphosphine Ligands in Thermally Activated Delayed Fluorescent Copper(I) Complexes: Impact on the Performance of Electroluminescence …
2021
We report a series of seven cationic heteroleptic copper(I) complexes of the form [Cu(P^P)(dmphen)]BF4, where dmphen is 2,9-dimethyl-1,10-phenanthroline and P^P is a diphosphine chelate, in which the effect of the bite angle of the diphosphine ligand on the photophysical properties of the complexes was studied. Several of the complexes exhibit moderately high photoluminescence quantum yields in the solid state, with ΦPL of up to 35%, and in solution, with ΦPL of up to 98%. We were able to correlate the powder photoluminescence quantum yields with the % Vbur of the P^P ligand. The most emissive complexes were used to fabricate both organic light-emitting diodes and light-emitting electrochem…
Enhancing the photoluminescence quantum yields of blue-emitting cationic iridium(iii) complexes bearing bisphosphine ligands
2016
EZ-C acknowledges the University of St Andrews for financial support. We thank Johnson Matthey and Umicore AG for the gift of materials and Cihang Yu for the preparation of isopropxantphos. We thank Dr. Nail Shaveleev for the synthesis of NMS25. IDWS and AKB acknowledge support from EPSRC (EP/J01771X). This work has been supported by the Spanish Ministry of Economy and Competitiveness (MINECO) MAT2014-55200. Herein we present a structure-property relationship study of thirteen cationic iridium (III) complexes of the form of [Ir(C^N)2(P^P)]PF6 in both solution and the solid state through systematic evaluation of six bisphosphine (P^P) ligands (xantphos, dpephos, dppe, Dppe, nixantphos and is…
Green phosphorescence and electroluminescence of sulfur pentafluoride-functionalized cationic iridium(III) complexes
2015
EZ-C acknowledges the University of St Andrews for financial support. We report four cationic iridium(III) complexes [Ir(C^N)2(dtBubpy)](PF6) that have sulfurpentafluoride-modified 1-phenylpyrazole and 2-phenylpyridine cyclometalating (C^N) ligands (dtBubpy = 4,4'-di-tert-butyl-2,2'-bipyridyl). Three of the complexes were characterized by single-crystal X-ray structure analysis. In cyclic voltammetry, the complexes undergo reversible oxidation of iridium(III) and irreversible reduction of the SF5 group. They emit bright green phosphorescence in acetonitrile solution and in thin films at room temperature, with emission maxima between 482–519 nm and photoluminescence quantum yields of up to 7…