Solute radical cation yields in the pulse radiolysis of solutions of aromatic amines in chlorinated hydrocarbons

Burrows, Hugh D.; Greatorex, D.; Kemp, Terence J.

doi:10.1021/j100645a004

Cited by 58 publications

(31 citation statements)

References 3 publications

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“…This is in agreement with gamma radiolysis studies on halogenated alkanes in alkane glasses at 77 K, where the halocarbon radical cation has a band around 370 nm [28]. From the known radiation chemistry of chloroform [22,27], the species absorbing at 560 nm (2.21 eV) is assigned unambiguously to the po-sitive charge carrier (also described as positive polaron or radical cation) of PF2/6 formed by one-electron oxidation by chloroform radical cation in the reaction sequence…”

Section: Resultssupporting

confidence: 87%

“…In our experiments, from the polymer molar concentration and the yield of solvent radical cation, there is always less than one positive charge (hole) per chain (low radiation doses). Using TTA as dosimeter, and taking a molar absorption coefficient for TTA radical cation ¼ 21 900 M À1 cm À1 from [27], a molar absorption coefficient was determined for the positively charged PF2/6 species. The difficulties of defining a molar absorption coefficient for conjugated polymers have been discussed in detail elsewhere [32], and we have chosen to express polymer concentrations in terms of the number of conjugation segments, which are given by the number of positive charges accepted by the polymer.…”

Section: Resultsmentioning

confidence: 99%

“…The general spectrometer design is similar to that in [26]. Dosimetry measurements were made with argon saturated solutions of tri(p-tolyl)amine (TTA, 10 mM) in chloroform [27].…”

Section: Methodsmentioning

confidence: 99%

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Hole formation and transfer in poly[9,9-di(ethylhexyl)fluorene] and an amine end-capped derivative in solution

Burrows

Melo

Förster

et al. 2004

Chemical Physics Letters

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Pulse radiolysis has been used to study the positively charged state of isolated chains of poly[9,9-di(ethylhexyl)fluorene] in chloroform solution. This is found to have an absorption maximum at 560 nm and a weaker band around 420 nm. Intermolecular electron transfer is observed from the aromatic amine tri(p-tolylamine) to this species. With the corresponding polyfluorene derivative end-capped by an arylamine, intramolecular transfer of electrons from the triphenylamine end-cap to the positively charged polyfluorene chain is found on timescales faster than the detection time of the system (ca. 500 ns).

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Section: Resultssupporting

confidence: 87%

Section: Resultsmentioning

confidence: 99%

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Hole formation and transfer in poly[9,9-di(ethylhexyl)fluorene] and an amine end-capped derivative in solution

Burrows

Melo

Förster

et al. 2004

Chemical Physics Letters

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“…As the transient absorption pattern of the oxidized and reduced forms of the cluster reference compound 3 were unknown, these transients were generated by electron pulse radiolysis. The oxidized form of the cluster was formed by radiolysis of a solution of 3 in CH 2 Cl 2 with short electron pulses generating the radical cation of CH 2 Cl 2 14 and further oxidizing the cluster via bimolecular electron transfer according to Scheme .…”

Section: Resultsmentioning

confidence: 99%

An Electrochemical and Photophysical Study of a Covalently Linked Inorganic–Organic Dyad

et al. 2010

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A molecular donor-acceptor dyad comprising a hexarhenium cluster core, [Re(6)(mu(3)-Se)(8)](2+), and a fullerene moiety which are covalently linked through a pyridine ligand was synthesized and fully characterized. The electrochemical and photophysical properties are reported. The detailed study includes cyclic voltammetry, steady-state absorption and fluorescence spectroscopy, radiation chemistry and transient absorption spectroscopy. A light-induced electron transfer between the inorganic cluster moiety and the fullerene can be excluded. However, a light-induced energy transfer from the rhenium cluster to the fullerene is proposed.

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“…However, although valuable information has been obtained from these studies, the relatively long timescale between mixing of reagents and observation of spectra leads to the possibility of multistep processes and observation of higher oxidation states. Radiolysis of solutes in chloroform solution has been shown [45,46] to be a good route for speci®cally generating their one-electron oxidised species, S z1 , in the reaction sequence…”

Section: Positive Charge Carriersmentioning

confidence: 99%

Transient absorption spectra of triplet states and charge carriers of conjugated polymers

Miguel

Monkman

Hamblett

et al. 2001

Journal of Molecular Structure

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The use of pulse radiolysis to study transient species in conjugated polymers in solutions is discussed, with particular reference to poly(2-methoxy-5-(2 0 -ethylhexoxy)-p-phenylenevinylene) (MEH-PPV). The excited triplet state is speci®cally generated by energy transfer on radiolysis of benzene solutions in the presence of suitable sensitisers, and its spectrum is reported. The presence of vibronic structure suggests a localised triplet state. By varying the energy of the sensitiser, it is possible to determine the energy of the lowest triplet state. Results are also presented for the triplet±triplet absorptions and energies of ®ve other common p-conjugated polymers. The MEH-PPV triplet absorption, produced on radiolysis, does not increase linearly with either polymer concentration or radiation dose. This is suggested to be due to the presence of multiple triplet excitations on the isolated polymer chains. Intrachain triplet±triplet annihilation is observed, and is seen to lead to delayed¯uorescence. Spectra are also reported for the positive and negative charge carriers of MEH-PPV and the other polymers speci®cally produced by pulse radiolysis of the polymers in chloroform or tetrahydrofuran solutions. q

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Solute radical cation yields in the pulse radiolysis of solutions of aromatic amines in chlorinated hydrocarbons

Cited by 58 publications

References 3 publications

Hole formation and transfer in poly[9,9-di(ethylhexyl)fluorene] and an amine end-capped derivative in solution

Hole formation and transfer in poly[9,9-di(ethylhexyl)fluorene] and an amine end-capped derivative in solution

An Electrochemical and Photophysical Study of a Covalently Linked Inorganic–Organic Dyad

Transient absorption spectra of triplet states and charge carriers of conjugated polymers

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