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Radical Cation (radical + cation)

Distribution by Scientific Domains

Chemistry	87%
Polymers and Materials Science	2%
2 Other Domains	11%

Distribution within Chemistry

General & Introductory Chemistry	32%
Mass Spectrometry	19%
Computational Chemistry & Molecular Modeling	13%
Organic Chemistry	11%
Analytical Chemistry	2%
5 Other Subdomains	23%

Selected Abstracts

Radical Cation and Dication Derived from 4,8-Diethylbenzo[1,2- d:4,5- d,]bis[1,2,3]trithiole [DEBBT]: Change of Electronic State from Singlet-State Dication DEBBT(2+)- S to Triplet-State Dimer 2DEBBT(2+)- T in D2SO4 and CD3CN Solutions

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 24 2003
Takeshi Kimura
Abstract 4,8-Diethylbenzo[1,2- d:4,5- d,]bis[1,2,3]trithiole [DEBBT] was oxidized using concentrated D2SO4, leading to the generation of the radical cation DEBBT(·+) which was verified by ESR spectroscopy. DEBBT(·+) in the solution was further oxidized to produce the dication DEBBT(2+), as determined by 1H and 13C NMR spectroscopy. DEBBT(2+) was also prepared by treating DEBBT 1-oxide [DEBBT 1-O] with concentrated D2SO4, and was verified by 1H and 13C NMR spectroscopy. The 13C NMR chemical shifts of DEBBT(2+), calculated by the density functional theoretical (DFT) method at the B3LYP6-31G** level, correlated well with those obtained experimentally. The ESR signal of DEBBT(2+) generated from DEBBT 1-O was observed in solution, which implies that the singlet-state dication DEBBT(2+)- S isomerizes to the triplet-state dication DEBBT(2+)- T, and that two molecules of DEBBT(2+)- T further form a spin pair at one trithiole ring with significant distance between the two radical centers. The oxidation of DEBBT with one or two equivalents of single-electron oxidizing reagents produced DEBBT(·+) and DEBBT(2+), and the salts were isolated in a stable form. However, the DEBBT(2+) that was prepared by oxidation with NOPF6 proved silent for NMR in CD3CN, while ESR was active. The stability, electronic state, and NMR and ESR spectroscopy of the dication are affected by solvation with D2SO4 and CD3CN. The optimized structures and the total energy of the singlet- and triplet-state dication were calculated using the DFT method at the B3LYP6-31G** level, which shows that the structures of the singlet- and triplet-state dications have a completely planar form with 1.7 kcal/mol as the total energy difference between them. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]

Isolation of a Carbene-Stabilized Phosphorus Mononitride and Its Radical Cation (PN+.),

ANGEWANDTE CHEMIE, Issue 34 2010
Rei Kinjo Dr.
Carbene stechen Metalle aus: Phosphormononitrid-Übergangsmetall-Komplexe wurden bisher nicht isoliert, doch ein PN-Fragment mit zwei sperrigen, stark elektronenschiebenden Singulettcarbensubstituenten lässt sich bei Raumtemperatur synthetisieren (siehe Bild; P,rot, N,blau, C,grau). Einelektronenoxidation lieferte das entsprechende stabile Radikalkation. [source]

A Spiro-Fused Triarylaminium Radical Cation with a Triplet Ground State,

ANGEWANDTE CHEMIE, Issue 32 2009
Akihiro Ito Dr.
No abstract is available for this article. [source]

Strong Evidence for an Unprecedented Borderline Case of Dissociation and Cycloaddition in Open-Shell 1,3-Dipole Chemistry: Transient Nitrilium Phosphane-Ylide Complex Radical Cations

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2009
Holger Helten
Abstract The reaction of 3-ferrocenyl-substituted 2H -azaphosphirene complexes 1a,c in the presence of substoichiometric amounts of ferrocenium hexafluorophosphate yields 3,5-diferrocenyl-substituted 2H -1,4,2-diazaphosphole complexes 3a,c and difluoro(organo)phosphane complexes 4a,c. The reaction of 1a,c and [FcH]PF6 with cyanoferrocene yields 3a,c in a straightforward way. The molecular structures of 3a,c were unambiguously identified by multinuclear NMR spectroscopic experiments, mass spectrometry, and single-crystal X-ray diffraction studies. DFT calculations on model complexes 1d,m and 3d,m reveal a close similarity of Mo and W complexes (vs. Cr) and a strong influence of the ferrocenyl substituent on the geometry, spin, and charge distribution of reactive intermediates and the reaction course. Strong support for the assumption of a dissociation,cycloaddition reaction sequence leading to 3 and thus a surprising "cannibalistic" reaction was obtained.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

Synthesis and Characterization of Radical Cations Derived from Mono- and Biferrocenyl-Substituted 2-Aza-1,3-butadienes: A Study of the Influence of an Asymmetric and Oxidizable Bridge on Intramolecular Electron Transfer

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2005
Vega Lloveras
Abstract The synthesis and study of structural and electronic properties of mono-ferrocenyl ,-conjugated complexes 5a,d, whose electronic characteristics have been systematically varied by introducing an electron-donating or electron-withdrawing substituent either at the 1-position or at the 4-position of the 2-aza-1,3-butadiene moiety linked to the ferrocenyl unit, are presented. The structural and electronic properties of the homobimetallic complex 5f, with two ferrocene units linked through the asymmetric and oxidizable 2-aza-1,3-butadiene bridge, is also reported. The crystal structures of complexes 5b, 5d, and 5f show a large degree of conjugation in this family of compounds. Complexes 5 show a rich electrochemical behavior due both to the oxidation of ferrocenyl units and the 2-aza-1,3-butadiene bridge, as revealed by cyclic voltammetry. Radical cations 5+· were prepared from 5 by coulometric oxidations following their generation by absorption spectroscopy. The electronic properties of all reported neutral and oxidized ,-conjugated complexes have been investigated by means of UV/Vis,near-IR, EPR and 57Fe Mössbauer spectroscopy. The detailed study of mono-oxidized species 5a+·,5f+· has permitted the determination of the influence of an asymmetric bridge with an electroactive character on the intramolecular electron transfer (IET) phenomenon, thus demonstrating that the 2-aza-1,3-butadiene bridge promotes the IET between the two metallic units of 5f+· through two different pathways. The experimental data and conclusions are supported by DFT computations (B3LYP/3-21G*) and time-dependent DFT methods. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Long-Lived Radical Cations of Monocyclic Arenes at Room Temperature Obtained by NbF5 Acting as an Oxidizing Agent and Counterion Precursor,

ANGEWANDTE CHEMIE, Issue 31 2010
Fabio Marchetti Dr.
Das Salz der Erde: Eine Reaktion, in der Niobpentafluorid als Oxidationsmittel (Bildung von NbF4) und als Fluoridakzeptor (Bereitstellung des Gegenions [Nb2F11],) fungiert, lieferte Radikalkationensalze von monocyclischen Arenen, einschließlich Benzol (siehe Bild). Anion-,-Wechselwirkungen sind entscheidend für die einzigartige Inertheit der Radikalkationen. [source]

Generation and Trapping of Alkene Radical Cations under Nonoxidizing Conditions: Formation of Six-Membered Rings by exo- and endo-Mode Cyclizations.

CHEMINFORM, Issue 48 2002
David Crich
Abstract For Abstract see ChemInform Abstract in Full Text. [source]

Synthesis and Characterization of Radical Cations Derived from Mono- and Biferrocenyl-Substituted 2-Aza-1,3-butadienes: A Study of the Influence of an Asymmetric and Oxidizable Bridge on Intramolecular Electron Transfer

ChemInform Abstract: Naphthidine Di(radical Cation)s-Stabilized Palladium Nanoparticles for Efficient Catalytic Suzuki,Miyaura Cross-Coupling Reactions.

CHEMINFORM, Issue 24 2008
Christophe Desmarets
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]

Six-Membered N-Heterocyclic Carbenes with a 1,1,-Ferrocenediyl Backbone: Bulky Ligands with Strong Electron-Donor Capacity and Unusual Non-Innocent Character

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 31 2009
Ulrich Siemeling
Abstract The stable, crystalline N-heterocyclic diaminocarbene fc[N(CH2tBu)-C-N(CH2tBu)] (2d, fc = 1,1,-ferrocenediyl) was prepared by deprotonation of its formamidinium precursor fc[N(CH2tBu)-CH-N(CH2tBu)][BF4] (1d) and used for the preparation of the 16 valence electron complexes [Mo(2d)(CO)4], [RhCl(2d)(cod)] (cod = 1,5-cyclooctadiene) and [RhCl(2d)(CO)2]. 1d, 2d and [RhCl(2d)(cod)] were structurally characterised by single-crystal X-ray diffraction studies. The electrochemical properties of 2d, its 2-adamantyl analogue 2c, its complex [RhCl(2d)(CO)2] and of the precursors 1d and 1,1,-bis(neopentylamino)ferrocene were investigated by electrochemistry. The carbenes are easily oxidised to the corresponding radical cation, whose persistent nature is unprecedented in the chemistry of N-heterocyclic carbenes. The spin density is located at the Fe atom and the carbene C atom according to the results of EPR spectroscopic studies and DFT calculations.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

Synthesis and Photophysical Properties of a Pyrazolino[60]fullerene with Dimethylaniline Connected by an Acetylene Linkage

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 10 2006
Andreas Gouloumis
Abstract A new triad based on pyrazolino[60]fullerene and a conjugated dimethylaniline group has been synthesized by a copper-free Sonogashira cross-coupling reaction using microwave irradiation as the source of energy. The electrochemical and photophysical properties of the triad were systematically investigated by techniques such as time-resolved fluorescence and transient absorption spectroscopy. Charge separation via the excited singlet state of the C60 moiety was confirmed in polar and nonpolar solvents and competes with triplet formation of the C60 moiety. The charge-separated state persisted for 91 ns. Such long lifetimes are characteristic of long distances between the radical anion of the pyrazolino[60]fullerene derivative and the radical cation of the dimethylaniline moiety. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Efficient Photosensitized Splitting of Thymine Dimer by a Covalently Linked Tryptophan in Solvents of High Polarity

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 6 2005
Qin-Hua Song
Abstract Tryptophan-thymine dimer model compounds used to mimic the repair reaction of DNA photolyase have been synthesized. The photosensitized cleavage of the dimer by the covalently linked tryptophan is strongly solvent-dependent with the reaction rates increasing in increasingly polar solvents, for example, the quantum yield , = 0.004 in THF/hexane (5:95) and 0.093 in water. The fluorescence of the tryptophan residue is quenched by the dimer moiety by electron transfer from the excited tryptophan to the dimer. Fluorescence-quenching studies indicated that the electron transfer was efficient in polar solvents. The splitting efficiency of the dimer radical anion within the tryptophan·+,dimer·, species is also remarkably solvent-dependent and increases with the polarity of the solvents. The back-electron-transfer reaction in the charge-separated species, which competes with cleavage, was suppressed in polar solvents. These results are in contrast to those of earlier solvent-dependent studies of indole-dimer systems, but they can be rationalized in terms of the differences in the distances between the chromophore unit and the attached dimer. The pH-dependent measurements of the splitting reaction and the deuterium isotope effect showed that the tryptophan radical cation within the charge-separated species does not deprotonate prior to the cleavage of the dimer radical anion. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source]

Formation and decay of the ABTS derived radical cation: A comparison of different preparation procedures

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 12 2002
Carola Henriquez
Bleaching of a preformed solution of the blue-green radical cation 2,2,-azinobis (3-ethylbenzothizoline-6-sulfonic acid) (ABTS+·) has been extensively used to evaluate the antioxidant capacity of complex mixtures and individual compounds. The reaction of the preformed radical with free-radical scavengers can be easily monitored by following the decay of the sample absorbance at 734 nm. The ABTS radical cation can be prepared employing different oxidants. Results obtained using MnO2 as oxidant show that the presence of manganese ions increases the rate of [ABTS]+· autobleaching in a concentration-dependent manner. The radicals can also be obtained by oxidizing ABTS with 2,2, -azobis(2-amidinopropane)hydrochloride (AAPH) or peroxodisulfate (PDS). The oxidation by AAPH takes place with a large activation energy and a low reaction order in ABTS. The data support a mechanism in which the homolysis of AAPH is the rate-limiting step, followed by the reaction of ABTS with the peroxyl radicals produced after the azocompound thermolysis. On the other hand, the low activation energy measured employing PDS, as well as the kinetic law, are compatible with the occurrence of a bimolecular reaction between the oxidant and ABTS. Regarding the use of ABTS-based methodologies for the evaluation of free radical scavengers, radical cations obtained employing AAPH as oxidant can be used only at low temperatures, conditions where further decomposition of the remaining AAPH is minimized. The best results are obtained with ABTS derived radicals generated in the reaction of PDS with an ABTS/PDS concentration ratio equal (or higher) to two. However, even with radicals prepared by this procedure, stoichiometric coefficients considerably larger than two are obtained for the consumption of the radical cation employing tryptophane or p -terbutylphenol as reductants. This casts doubts on the use of ABTS-based procedures for the estimation of antioxidant capacities. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 659,665, 2002 [source]

Spontaneous and catalyzed isomerizations of the acetamide radical cation

JOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 1 2001
Philippe Mourgues
No abstract is available for this article. [source]

Triplet state and phenoxyl radical formation of 3, 4-methylenedioxy phenol: a combined laser flash photolysis and pulse radiolysis study

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 3 2007
Ravi Joshi
Abstract Formations of triplet state, molecular cation radical, and phenoxyl radical of 3,4-methylenedioxy phenol (sesamol, SOH) in organic solvents have been investigated by laser photolysis as well as pulse radiolysis techniques. Photolysis of SOH in cyclohexane has been found to produce both triplet state (,max,,,480,nm) and phenoxyl radical (425,430,nm) of SOH by mono-photonic processes. However, radical cation (,max,=,450,nm) and phenoxyl radical of SOH have been observed on radiolysis in cyclohexane. Further, radiolysis of SOH in benzene has been found to produce phenoxyl radical only. Mechanism of phenoxyl radical formation by photo-excitation of SOH has been studied and triplet energy level of SOH is estimated to lie between 1.85 and 2.64,eV. Copyright © 2007 John Wiley & Sons, Ltd. [source]

Synthesis and photochemistry of a carotene,porphyrin,fullerene model photosynthetic reaction center

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 9 2004
Gerdenis Kodis
Abstract A new photosynthetic reaction center mimic consisting of a porphyrin (P) linked to both a fullerene electron acceptor (C60) and a carotenoid secondary electron donor (C) was synthesized and studied in 2-methyltetrahydrofuran using transient spectroscopic methods. Excitation of the porphyrin is followed by photoinduced electron transfer to the fullerene (,,=,32,ps) to yield C,P·+,C60·,. Electron transfer from the carotene to the porphyrin radical cation (,,=,125,ps) gives a final C·+,P,C60·, state with an overall yield of 0.95. This state decays to give the carotenoid triplet state with a time constant of 57,ns. The molecular triad is highly soluble in organic solvents and readily synthesized. These qualities make the molecule a useful artificial photosynthetic reaction center for a variety of spectroscopic and photochemical investigations. Copyright © 2004 John Wiley & Sons, Ltd. [source]

Rapid identification and preparative isolation of antioxidant components in licorice

JOURNAL OF SEPARATION SCIENCE, JSS, Issue 4-5 2010
Yeon Sil Lee
Abstract This study employed the online HPLC-2,2,-azinobis-(3-ethylbenzothiazoline-6-sulfonate radical cation (ABTS+·) bioassay to rapidly determine antioxidant compounds occurring in the licorice extract of Glycyrrhiza uralensis. The negative peaks of the ABTS+· radical scavenging detection system, which indicated the presence of antioxidant activity, were monitored by measuring the decrease in absorbance at 734,nm. The ABTS+ -based antioxidant activity profile showed that three peaks exhibited antioxidant activity, and then the high-speed counter-current chromatography technique of preparative scale was successfully applied to separate the three peaks I-III in one step from the licorice extract. The high-speed counter-current chromatography was performed using a two-phase solvent system composed of n -hexane,ethyl acetate,methanol,water (6.5:5.5:6:4, v/v). Yields of the three peaks, dehydroglyasperin C (I, 95.1% purity), dehydroglyasperin D (II, 96.2% purity), and isoangustone A (III, 99.5% purity), obtained were 10.33, 10.43, and 6.7% respectively. Chemical structures of the purified dehydroglyasperin C (I), dehydroglyasperin D (II), and isoangustone A (III) were identified by ESI-MS and 1H- and 13C-NMR analysis. [source]

Kinetic simulation studies on the transient formation of the oxo-iron(IV) porphyrin radical cation during the reaction of iron(III) tetrakis-5,10,15,20-(N-methyl-4-pyridyl)-porphyrin with hydrogen peroxide in aqueous solution

LUMINESCENCE: THE JOURNAL OF BIOLOGICAL AND CHEMICAL LUMINESCENCE, Issue 5 2003
Tapan Kumar Saha
Abstract High-valent oxo-iron(IV) species are commonly proposed as the key intermediates in the catalytic mechanisms of iron enzymes. Water-soluble iron(III) tetrakis-5,10,15,20-(N-methyl-4-pyridyl)porphyrin (Fe(III)TMPyP) has been used as a model of heme-enzyme to catalyse the hydrogen peroxide (H2O2) oxidation of various organic compounds. However, the mechanism of the reaction of Fe(III)TMPyP with H2O2 has not been fully established. In this study, we have explored the kinetic simulation of the reaction of Fe(III)TMPyP with H2O2 and of the catalytic reactivity of FeTMPyP in the luminescent peroxidation of luminol. According to the mechanism that has been established in this work, Fe(III)TMPyP is oxidized by H2O2 to produce (TMPyP)·+Fe(IV)=O (k1 = 4.5 × 104/mol/L/s) as a precursor of TMPyPFe(IV)=O. The intermediate, (TMPyP)·+Fe(IV)=O, represented nearly 2% of Fe(III)TMPyP but it does not accumulate in suf,cient concentration to be detected because its decay rate is too fast. Kinetic simulations showed that the proposed scheme is capable of reproducing the observed time courses of FeTMPyP in various oxidation states and the decay pro,les of the luminol chemiluminescence. It also shows that (TMPyP)·+Fe(IV)=O is 100 times more reactive than TMPyPFe(IV)=O in most of the reactions. These two species are responsible for the initial sharp and the sustained luminol emissions, respectively. Copyright © 2003 John Wiley & Sons, Ltd. [source]

ESR/DFT study of bis-iminophosphorane cation radicals

MAGNETIC RESONANCE IN CHEMISTRY, Issue 12 2007
Adil Matni
Abstract Bis-iminophosphoranes containing various types of linkers between two R3PN moieties were electrochemically oxidized at controlled potential in situ in the electron spin resonance (ESR) cavity. For linkers constituted of phenylenes, conjugated phenylenes or merely a dicyanoethylenic bond, this oxidation led to well-resolved ESR spectra which were characterized by their g values and by their 1H, 14N and 31P isotropic hyperfine constants. These coupling constants agree with those calculated by DFT for the corresponding cation radicals. Experimental and theoretical results clearly indicate that in these species the unpaired electron is mostly delocalized on the bridge and on the nitrogen atoms while the spin density on the phosphorus atoms is particularly small. Cyclic voltammetry and ESR spectra show that the nature of the bridge between the two iminophosphoranes considerably influences the oxidation potential of the compound as well as the stability of the radical cation. Information about the conformation of the precursor containing two Ph3PN moieties separated by a C(CN)C(CN)group was obtained from its crystal structure. Copyright © 2007 John Wiley & Sons, Ltd. [source]

Paracetamol (Acetaminophen): mechanisms of action

PEDIATRIC ANESTHESIA, Issue 10 2008
BRIAN J. ANDERSON PhD FANZCA FJFICM
Summary Paracetamol has a central analgesic effect that is mediated through activation of descending serotonergic pathways. Debate exists about its primary site of action, which may be inhibition of prostaglandin (PG) synthesis or through an active metabolite influencing cannabinoid receptors. Prostaglandin H2 synthetase (PGHS) is the enzyme responsible for metabolism of arachidonic acid to the unstable PGH2. The two major forms of this enzyme are the constitutive PGHS-1 and the inducible PGHS-2. PGHS comprises of two sites: a cyclooxygenase (COX) site and a peroxidase (POX) site. The conversion of arachidonic acid to PGG2 is dependent on a tyrosine-385 radical at the COX site. Formation of a ferryl protoporphyrin IX radical cation from the reducing agent Fe3+ at the POX site is essential for conversion of tyrosine-385 to its radical form. Paracetamol acts as a reducing cosubstrate on the POX site and lessens availability of the ferryl protoporphyrin IX radical cation. This effect can be reduced in the presence of hydroperoxide-generating lipoxygenase enzymes within the cell (peroxide tone) or by swamping the POX site with substrate such as PGG2. Peroxide tone and swamping explain lack of peripheral analgesic effect, platelet effect, and anti-inflammatory effect by paracetamol. Alternatively, paracetamol effects may be mediated by an active metabolite (p -aminophenol). p -Aminophenol is conjugated with arachidonic acid by fatty acid amide hydrolase to form AM404. AM404 exerts effect through cannabinoid receptors. It may also work through PGHS, particularly in areas of the brain with high concentrations of fatty acid amide hydrolase. [source]

Radical Cation Generation from Singlet and Triplet Excited States of All-trans-Lycopene in Chloroform,

PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 2 2004
Rui-Min Han
ABSTRACT On direct photoexcitation, subpicosecond time-resolved absorption spectroscopy revealed that the 1Bu -type singlet excited state of all- trans -lycopene in chloroform was about seven times more efficient than all-trans-,-carotene in generating the radical cation. The time constant of radical cation generation from the 1Bu -type state was found to be ,0.14 ps, a value that was comparable for the two carotenoids. On anthracene-sensitized triplet excitation, radical cation generation was found to be much less efficient for lycopene than for ,-carotene. A slow rising phase (20-30 ,s) in the bleaching of ground-state absorption was common for both lycopene and ,-carotene in chloroform and was ascribed to an efficient secondary reaction with a solvent radical leading to the formation of carotenoid radical cations. The reverse ordering in the tendency of the excited states of different multiplicities for the two carotenoids to generate radical cations is discussed in relation to the two carotenoids as scavengers of free radicals. [source]

A Photophysical and Photochemical Study of 6-Methoxy-2-naphthylacetic Acid, the Major Metabolite of the Phototoxic Nonsteroidal Antiinflammatory Drug Nabumetone

PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 2 2000
F. Boscá
ABSTRACT Nabumetone is a phototoxic nonsteroidal antiinflammatory drug used for the treatment of osteoarthritis. However, nabumetone is considered a prodrug with its metabolite 6-methoxy-2-naphthylacetic acid the active form. Photophysical and photochemical studies on this metabolite have been undertaken. It undergoes photodecarboxylation in aerated aqueous and organic solvents. In addition to the accepted photodegradation pathway for related molecules, a new mechanism that implies generation of the naphthalene radical cation from the excited singlet and addition of O2 prior to the decarboxylation process has been demonstrated. Evidence for the involvement of the excited singlet state in this mechanism have been obtained by steady-state and time-resolved fluorescence experiments. The fluorescence quenching by O2 and the shorter singlet lifetime in aerated solvents support this assignment. Laser flash photolysis also supports this mechanism by showing the noninvolvement of the triplet in the formation of the naphthalene radical cation. Finally, the well-known electron acceptor CCl4 acts as an efficient singlet quencher, enhancing the route leading to the radical cation, preventing intersystem crossing to the triplet and thus resulting in a dramatic increase in the yield of 6-methoxy-2-naphthaldehyde, the major oxidative decarboxylation product; this constitutes unambiguous proof in favor of the new mechanistic proposals. [source]

Can radical cations of the constituents of nucleic acids be formed in the gas phase using ternary transition metal complexes?,

RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 13 2005
Sheena Wee
Electrospray ionization (ESI) tandem mass spectrometry (MS/MS) of ternary transition metal complexes of [M(L3)(N)]2+ (where M,=,copper(II) or platinum(II); L3,=,diethylenetriamine (dien) or 2,2,:6,,2,-terpyridine (tpy); N,=,the nucleobases: adenine, guanine, thymine and cytosine; the nucleosides: 2,deoxyadenosine, 2,deoxyguanosine, 2,deoxythymine, 2,deoxycytidine; the nucleotides: 2,deoxyadenosine 5,-monophosphate, 2,deoxyguanosine 5,-monophosphate, 2,deoxythymine 5,-monophosphate, 2,deoxycytidine 5,-monophosphate) was examined as a means of forming radical cations of the constituents of nucleic acids in the gas phase. In general, sufficient quantities of the ternary complexes [M(L3)(N)]2+ could be formed for MS/MS studies by subjecting methanolic solutions of mixtures of a metal salt [M(L3)X2] (where M,=,Cu(II) or Pt(II); L3,=,dien or tpy; X,=,Cl or NO3) and N to ESI. The only exceptions were thymine and its derivatives, which failed to form sufficient abundances of [M(L3)(N)]2+ ions when: (a) M,=,Pt(II) and L3,=,dien or tpy; (b) M,=,Cu(II) and L3,=,dien. In some instances higher oligomeric complexes were formed; e.g., [Pt(tpy)(dG)n]2+ (n,=,1,13). Each of the ternary complexes [M(L3)(N)]2+ was mass-selected and then subjected to collision-induced dissociation (CID) in a quadrupole ion trap. The types of fragmentation reactions observed for these complexes depend on the nature of all three components (metal, auxiliary ligand and nucleic acid constituent) and can be classified into: (i) a redox reaction which results in the formation of the radical cation of the nucleic acid constituent, N+.; (ii) loss of the nucleic acid constituent in its protonated form; and (iii) fragmentation of the nucleic acid constituent. Only the copper complexes yielded radical cations of the nucleic acid constituent, with [Cu(tpy)(N)]2+ being the preferred complex due to suppression, in this case, of the loss of the nucleobase in its protonated form. The yields of the radical cations of the nucleobases from the copper complexes follow the order of their ionization potentials (IPs): G (lowest IP),>,A,>,C,>,T (highest IP). Sufficient yields of the radical cations of each of the nucleobases allowed their CID reactions (in MS3 experiments) to be compared to their even-electron counterparts. Copyright © 2005 John Wiley & Sons, Ltd. [source]

On the fragmentation pathway of the ionized enol of glycine in the gas phase

RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 8 2001
T. Marino
Density functional and second-order many body perturbation approaches were used to compute the potential energy surface for the fragmentation of the ionized enol of glycine [H2NCH,=,C(OH)2]+· into water and aminoketene radical cation [H2N-HC,=,CO]+·. Two possible pathways were considered. The potential energy surfaces obtained are very similar and both predict the existence of a molecular complex in which the water is coordinated to the aminoketene moiety in two different fashions with a noticeable binding energy. The fragmentation is kinetically controlled by the step in which the molecular complex is formed from the most stable cation enol of glycine. Our quantum-mechanical data confirm the hypothesis that the ylide ion [H3NCHCOOH]+· is an intermediate in the water loss. Copyright © 2001 John Wiley & Sons, Ltd. [source]

Tris(4-bromophenyl)aminium hexachloridoantimonate (`Magic Blue'): a strong oxidant with low inner-sphere reorganization

ACTA CRYSTALLOGRAPHICA SECTION C, Issue 7 2010
Mauricio Quiroz-Guzman
Both the radical cation tris(4-bromophenyl)aminium hexachloridoantimonate (`Magic Blue'), (C18H12Br3N)[SbCl6], (I), and neutral tris(4-bromophenyl)amine, C18H12Br3N, (II), show extremely similar three-bladed propeller structures with planar N atoms. Key geometric features, such as the C,N bond distances and the angles between the planes of the aryl groups and the central NC3 plane, are identical within experimental uncertainty in the two structures. This contrasts with the significant structural changes observed on oxidation of more electron-rich triarylamines, where resonance contributes to the stabilization of the radical cation, and suggests that, in general, more strongly oxidizing triarylaminium cations will have lower inner-sphere reorganization energies than their lower-potential analogues. [source]

Dendritic Porphyrin,Fullerene Conjugates: Efficient Light-Harvesting and Charge-Transfer Events

CHEMISTRY - A EUROPEAN JOURNAL, Issue 45 2009
Sebastian Schlundt
Abstract A novel dendritic C60 -H2P-(ZnP)3 (P=porphyrin) conjugate gives rise to the successful mimicry of the primary events in photosynthesis, that is, light harvesting, unidirectional energy transfer, charge transfer, and charge-shift reactions. Owing, however, to the flexibility of the linkers that connect the C60, H2P, and ZnP units, the outcome depends strongly on the rigidity/viscosity of the environment. In an agar matrix or Triton X-100, time-resolved transient absorption spectroscopic analysis and fluorescence-lifetime measurements confirm the following sequence. Initially, light harvesting is seen by the peripheral C60 -H2P- *(ZnP)3 conjugate. Once photoexcited, a unidirectional energy transfer funnels the singlet excited-state energy to H2P to form C60 -*(H2P)-(ZnP)3, which powers an intramolecular charge transfer that oxidizes the photoexcited H2P and reduces the adjacent C60 species. In the correspondingly formed (C60)., -(H2P).+ -(ZnP)3 conjugate, an intramolecular charge-shift reaction generates (C60)., -H2P-(ZnP)3.+, in which the radical cation resides on one of the three ZnP moieties, and for which lifetimes of up to 460,ns are found. On the other hand, investigations in organic media (i.e., toluene, THF, and benzonitrile) reveal a short cut, that is, the peripheral ZnP unit reacts directly with C60 to form (C60)., -H2P-(ZnP)3.+. Substantial configurational rearrangements, placing ZnP and C60 in proximity to each other,are, however, necessary to ensure the required through space interactions (i.e., close approach). Consequently, the lifetime of (C60)., -H2P-(ZnP)3.+ is as short as 100,ps in benzonitrile. [source]

Ferrocenyl-Ended Thieno,Vinylene Oligomers: Donor,Acceptor Polarization and Mixed-Valence Properties with Emphasis on the Raman Mapping of Localized-to-Delocalized Transitions

CHEMISTRY - A EUROPEAN JOURNAL, Issue 11 2009
Juan Casado Dr.
Abstract What's your role? New oligothiophene,vinylene compounds have been synthesized to study the role of the conjugated chain in two different cases (see scheme; MV=mixed valence). The electronic and molecular structures were analyzed by means of electronic, X-ray photoelectron, and Raman spectroscopy, together with thermo spectroscopy, electrochemistry, and DFT calculations. New oligothiophene,vinylene compounds have been synthesized in order to study the role of the conjugated chain in two different cases: 1),when push,pull action operates between an electron-donor and an electron-acceptor group at the ends of the thiophene,vinylene conjugated chain, and 2),when mixed-valence action is induced by single oxidation of the same chain functionalized at both terminal positions with ferrocene groups leading to competition between the donor groups. The electronic and molecular structures are analyzed by means of electronic, X-ray photoelectron and Raman spectroscopies, together with thermospectroscopy, electrochemistry and density functional theory calculations. The cyclic voltammetry processes have been followed by spectrochemistry. It is shown that the radical cation of the diferrocenyl derivative is a class,III mixed-valence system (i.e., fully delocalized) according to its Raman spectrum. Moreover, by Raman thermo-spectroscopy the thermal transition of this radical cation from a delocalized (class,III, room temperature) to a localized (class,II, ,160,°C) state is scanned. In all cases the Raman study is paralleled by an electronic absorption spectroscopic analysis. Structure,property relationships are proposed for molecules of two important fields of very active research as that of the non-linear optics (i.e., organic optoelectronic) and that of the mixed-valence systems (i.e., charge-transfer processes). [source]

Polysulfurated Pyrene-Cored Dendrimers: Luminescent and Electrochromic Properties

CHEMISTRY - A EUROPEAN JOURNAL, Issue 33 2008
Marc Gingras Prof.
Abstract We have synthesized a novel class of dendrimers, consisting of a polysulfurated pyrene core with appended poly(thiophenylene) dendrons (PyG0, PyG1, and PyG2, see Scheme,1), which exhibit remarkable photophysical and redox properties. In dichloromethane or cyclohexane solution they show a strong, dendron-localized absorption band with a maximum at around 260,nm and a band in the visible region with a maximum at 435,nm, which can be assigned to the pyrene core strongly perturbed by the four sulfur substituents. The dendrimers exhibit a strong (,=0.6), short-lived (,=2.5,ns) core-localized fluorescence band with maximum at approximately 460,nm in cyclohexane solution at 293,K. A strong fluorescence is also observed in dichloromethane solution at 293,K, in dichloromethane/chloroform rigid matrix at 77,K, and in the solid state (powder) at room temperature. The dendrimers undergo reversible chemical and electrochemical one-electron oxidation with formation of a strongly colored deep blue radical cation. A second, reversible one-electron oxidation is observed at more positive potential values. The photophysical and redox properties of the three dendrimers are finely tuned by the length of their branches. The strong blue fluorescence and the yellow to deep blue color change upon reversible one-electron oxidation can be exploited for optoelectronic devices. [source]

Synthesis and Photoinduced Electron-Transfer Properties of Phthalocyanine,[60]Fullerene Conjugates

CHEMISTRY - A EUROPEAN JOURNAL, Issue 12 2008
Maurizio Quintiliani Dr.
Abstract A series of three novel ZnPc,C60 conjugates (Pc=phthalocyanine) 1,a,c bearing different spacers (single, double, and triple bond) between the two electroactive moieties was synthesized and compared to that of ZnPc,C60 conjugate 2, in which the two electroactive moieties are linked directly. The synthetic strategy, towards the preparation of 1,a,c, involved palladium-catalyzed cross-coupling reactions over a monoiodophthalocyanine precursor 4 to introduce the corresponding spacer, and subsequent dipolar cycloaddition reaction to C60. Detailed photophysical investigations of 1,a,c and 2 prompted an intramolecular electron transfer that evolves from the photoexcited ZnPc to the electron-accepting C60. In particular, with the help of femtosecond laser photolysis charge separation was indeed confirmed as the major deactivation channel. Complementary time-dependent density functional calculations supported the spectral assignment, namely, the spectral identity of the ZnPc.+ radical cation and the C60., radical anion as seen in the differential absorption spectra. The lifetimes of the correspondingly formed radical ion-pair states depend markedly on the solvent polarity: they increase as polarity decreases. Similarly, although to a lesser extent, the nature of the linker impacts the lifetime of the radical ion-pair states. In general, the lifetimes of these states tend to be shortest in the system that lacks any spacer at all (2), whereas the longest lifetimes were found in the system that carries the triple-bond spacer (1,a). [source]

A Spectroscopic Study of the Reduction of Geometrically Restrained Viologens

CHEMISTRY - A EUROPEAN JOURNAL, Issue 28 2007
Andrew
Abstract A small series of N,N,-dimethyl-4,4,-bipyridinium dication derivatives (commonly known as viologens) has been synthesized and fully characterized; a short dialkoxy tether attached at the 3,3,-positions is used to alter the central dihedral angle. These angles were determined by both single-crystal X-ray diffraction and by computational studies made for the dication, radical cation, and neutral species in a solvent reservoir. The dihedral angle derived for the dication controls the first reduction potential, whereas the geometry of the resultant ,-radical cation determines the magnitude of the second reduction potential. The optical absorption spectra recorded for the various species, and especially those of the radical cations, and the EPR spectral parameters of the ,-radical cations also depend on the molecular geometry. In particular, the central dihedral angle influences the spin density distribution around the aromatic nucleus and, by way of comparison to the parent viologen, it has been possible to resolve the angle dependence from the inherent inductive effect of the strap. These results are considered in terms of the degree of electronic communication between the two aromatic rings, as controlled by the length of the tether. [source]