Search results for "phosphore"
showing 10 items of 114 documents
Synthèse et caractérisation de phosphine, borane, amine sur plateforme ferrocène polyfonctionnelle
2016
Ferrocene platforms are useful in coordination chemistry and catalysis thanks to their robustness and versatile functionalization. Ferrocene backbone allows the implantation of several key functional groups in a restricted space, inducing close proximity and potential polyfunctional cooperation (see for instance ferrocenyl polyphosphine chemistry). Ansa ferrocene and ferrocene bearing conformational control inducing groups maximizing the proximity of key groups have been widely reported.The first part of this thesis focuses on the synthesis of new borylated cyclopentadienyl, and their use in formation of borylated metallocenes bearing conformational constraints. NMR analysis and DFT calcula…
Photo-Activated Phosphorescence of Ultrafine ZnS:Mn Quantum Dots: On the Lattice Strain Contribution
2021
We address the enhancement of orange-light luminescence of Mn-doped zinc sulfide nanoparticles (NPs) induced by exposure to UV light. Ultrafine ZnS:Mn NPs are prepared by microwave-assisted crystal growth in ethanol, without adding any dispersant agents. When exposed to UV light, their orange emission intensity undergoes a strong increase. This effect is observed when the NPs are deposited as a thin layer on a transparent substrate or dispersed in an ethanolic suspension. Such a feature was already observed on polymer- or surfactant-coated ZnS:Mn NPs and explained as a passivation effect. In this study, by coupling X-ray photoelectron, Fourier transform infrared, and electron paramagnetic r…
Theoretical study of the dark photochemistry of 1,3-butadiene via the chemiexcitation of Dewar dioxetane.
2015
Excited-state chemistry is usually ascribed to photo-induced processes, such as fluorescence, phosphorescence, and photochemistry, or to bio-and chemiluminescence, in which light emission originates from a chemical reaction. A third class of excited-state chemistry is, however, possible. It corresponds to the photochemical phenomena produced by chemienergizing certain chemical groups without light - chemiexcitation. By studying Dewar dioxetane, which can be viewed as the combination of 1,2-dioxetane and 1,3-butadiene, we show here how the photo-isomerization channel of 1,3-butadiene can be reached at a later stage after the thermal decomposition of the dioxetane moiety. Multi-reference mult…
A theoretical study of the emission spectra of indole and its analogs: indene, benzimidazole, and 7-azaindole
2000
Abstract The complete active space (CAS) SCF method and multiconfigurational second-order perturbation theory (CASPT2) have been used to study the electronic spectra of indole, indene, benzimidazole, and 7-azaindole. The paper is focused on the study of the low-lying valence triplet and singlet electronic states at the optimized geometries of the excited states. The geometries have been optimized by using analytic CASSCF derivatives. CASPT2 point calculations have been performed in order to obtain band origins and relaxed emission energies. The results are analyzed in the context of the complex emission processes, both fluorescence and phosphorescence, displayed by the title compounds, whic…
Phosphorescent Pt II Systems Featuring Both 2,2′‐Dipyridylamine and 1,3,5‐Triazapentadiene Ligands
2014
The treatment of cis-[Pt(dpa)(RCN)2][SO3CF3]2 {dpa = 2,2′-dipyridylamine, R = Me, Et, CH2Ph, Ph; [2a–d](OTf)2} (OTf = SO3CF3) with 2 equiv. of N,N′-diphenylguanidine [NH=C(NHPh)2] in CH2Cl2 solutions at room temp. for 16 h gives [Pt(dpa){NH=C(R)NC(NHPh)=NPh}][SO3CF3] {[3a,b,d](OTf)} as the addition products and [Pt(dpa){NH=C(R)NHC(R)=NH}][SO3CF3]2 {[4a,b](OTf)2} as the tailoring products. The formulation of complexes [3a,b,d](OTf) and [4a,b](OTf)2 was supported by satisfactory C, H, and N elemental analyses and agreeable high-resolution ESI-MS, IR, and 1H (including 1H–1H COSY experiments) and 13C{1H} NMR data. The structures of all of the platinum species were determined by single-crystal …
Bright Blue Phosphorescence from Cationic Bis-Cyclometalated Iridium(III) Isocyanide Complexes
2012
We report new bis-cyclometalated cationic indium(III) complexes [((CN)-N-boolean AND)(2)Ir(CN-tert-Bu)(2)](CF3SO3) that have tert-butyl isocyanides as neutral auxiliary ligands and 2-phenylpyridine or 2-(4'-fluoropheny1)-R-pyridines (where R is 4-methoxy, 4-tert-butyl, or 5-trifluoromethyl) as (CN)-N-boolean AND ligands. The complexes are white or pale yellow solids that show irreversible reduction and oxidation processes and have a large electrochemical gap of 3.58-3.83 V. They emit blue or bluegreen phosphorescence in liquid/solid solutions from a cyclometalating-ligand-centered excited state. Their emission spectra show vibronic structure with the highest-energy luminescence peak at 440-…
Excited state decay of cyclometalated polypyridine ruthenium complexes: insight from theory and experiment.
2016
Deactivation pathways of the triplet metal-to-ligand charge transfer ((3)MLCT) excited state of cyclometalated polypyridine ruthenium complexes with [RuN5C](+) coordination are discussed on the basis of the available experimental data and a series of density functional theory calculations. Three different complex classes are considered, namely with [Ru(N^N)2(N^C)](+), [Ru(N^N^N)(N^C^N)](+) and [Ru(N^N^N)(N^N^C)](+) coordination modes. Excited state deactivation in these complex types proceeds via five distinct decay channels. Vibronic coupling of the (3)MLCT state to high-energy oscillators of the singlet ground state ((1)GS) allows tunneling to the ground state followed by vibrational rela…
Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(iii) complex I: synthesis, spectroscopy and static quantum chemistry.
2021
In spite of intense, recent research efforts, luminescent transition metal complexes with Earth-abundant metals are still very rare owing to the small ligand field splitting of 3d transition metal complexes and the resulting non-emissive low-energy metal-centered states. Low-energy excited states decay efficiently non-radiatively, so that near-infrared emissive transition metal complexes with 3d transition metals are even more challenging. We report that the heteroleptic pseudo-octahedral d2-vanadium(iii) complex VCl3(ddpd) (ddpd = N,N′-dimethyl-N,N′-dipyridine-2-yl-pyridine-2,6-diamine) shows near-infrared singlet → triplet spin–flip phosphorescence maxima at 1102, 1219 and 1256 nm with a …
ChemInform Abstract: Excited State Decay of Cyclometalated Polypyridine Ruthenium Complexes: Insight from Theory and Experiment
2016
Deactivation pathways of the triplet metal-to-ligand charge transfer (3MLCT) excited state of cyclometalated polypyridine ruthenium complexes with [RuN5C]+ coordination are discussed on the basis of the available experimental data and a series of density functional theory calculations. Three different complex classes are considered, namely with [Ru(N^N)2(N^C)]+, [Ru(N^N^N)(N^C^N)]+ and [Ru(N^N^N)(N^N^C)]+ coordination modes. Excited state deactivation in these complex types proceeds via five distinct decay channels. Vibronic coupling of the 3MLCT state to high-energy oscillators of the singlet ground state (1GS) allows tunneling to the ground state followed by vibrational relaxation (path A…
Harvesting Fluorescence from Efficient Tk -> Sj (j, k > 1) Reverse Intersystem Crossing for ??* Emissive Transition-Metal Complexes
2013
Using a bimetallic Au(I) complex bearing alkynyl-(phenylene)3-diphosphine ligand (A-3), we demonstrate that the fluorescence can be exquisitely harvested upon T1 → Tk (k > 1) excitation followed by Tk → Sj (j, k > 1) intersystem crossing (ISC) back to the S1 state. Upon S0 → S1 355 nm excitation, the S1 → T1 intersystem crossing rate has been determined to be 8.9 × 108 s–1. Subsequently, in a two-step laser pump–probe experiment, following a 355 nm laser excitation, the 532 nm T1 → Tk probing gives the prominent blue 375 nm fluorescence, and this time-dependent pump–probe signal correlates well with the lifetime of the T1 state. Careful examination reveals the efficiency of Tk → Sj (j, k > …