Temperature effect on the competition between the processes of 9-cyanophenanthrene exciplex decay

Dogadkin, D. N.; Dolotova, E. V.; Соболева, И. В.; Kuz’min, M. G.; Plyusnin, Victor F.; Pozdnyakov, Ivan P.; Grivin, Vjacheslav P.

doi:10.1007/s10733-005-0004-7

Cited by 3 publications

(2 citation statements)

References 24 publications

(39 reference statements)

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“…Envelopes of exciplex emission spectra as well as rates of internal conversion and intersystem crossing are governed by inhomogeneous broadening σ rather than by reorganization energy λ S . Experimental data reveal a very small temperature effect on exciplex decay lifetimes (activation enthalpy less than 1−5 kJ mol -1 ) , thereby confirming activationless quantum transition mechanism of exciplex decay. Parameters h ν V , σ, S , and λ V have practically the same values for exciplexes and SSRIP suggesting that dominant accepting vibrational modes for these species are identical.…”

Section: Discussionmentioning

confidence: 64%

The Behavior of Exciplex Decay Processes and Interplay of Radiationless Transition and Preliminary Reorganization Mechanisms of Electron Transfer in Loose and Tight Pairs of Reactants

2006

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Exciplex emission spectra and rate constants of their decay via internal conversion and intersystem crossing are studied and discussed in terms of conventional radiationless transition approach. Exciplexes of 9-cyanophenanthrene with 1,2,3-trimethoxybenzene and 1,3,5-trimethoxybenzene were studied in heptane, toluene, butyl acetate, dichloromethane, butyronitrile, and acetonitrile. A better description of spectra and rate constants is obtained using 0-0 transition energy and Gauss broadening of vibrational bands rather than the free energy of electron transfer and reorganization energy. The coincidence of parameters describing exciplex emission spectra and dependence of exciplex decay rate constants on energy gap gives the evidence of radiationless quantum transition mechanism rather than thermally activated medium reorganization mechanism of charge recombination in exciplexes and excited charge transfer complexes (contact radical ion pairs) as well as in solvent separated radical ion pairs. Radiationless quantum transition mechanism is shown to provide an appropriate description also for the main features of exergonic excited-state charge separation reactions if fast mutual transformations of loose and tight pairs of reactants are considered. In particular, very fast electron transfer (ET) in tight pairs of reactants with strong electronic coupling of locally excited and charge transfer states can prevent the observation of an inverted region in bimolecular excited-state charge separation even for highly exergonic reactions.

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Section: Discussionmentioning

confidence: 64%

The Behavior of Exciplex Decay Processes and Interplay of Radiationless Transition and Preliminary Reorganization Mechanisms of Electron Transfer in Loose and Tight Pairs of Reactants

2006

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“…Exciplexes are excited state complexes between an electron donor (D) and an electron acceptor (A) molecule stabilised in non-polar solvents, where the electron transfer becomes reversible. 1 The literature data indicates that many times the D molecule contains a nitrogen atom [2][3][4][5] or a methoxy group, [6][7][8] among other cases. Exciplexes are intensely studied for their applications as OLED materials [9][10][11][12][13][14] and sensors.…”

Section: Introduction *mentioning

confidence: 99%

Exciplex formation in the phenoxathiin-thioxanthone system

Tablet¹,

Ionescu²

2021

Rev.Roum.Chim.

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Amines and other nitrogen-containing compounds, due to their electron donor character, can form excited state emissive complexes in systems that comprise an electron acceptor. Sulphur-containing heteroaromatic compounds such as phenoxathiin are also well-known for their electron donor character. Starting from these two considerations, we aimed at finding exciplexes in which the electron donor contains sulphur. We studied several D-A pairs in solvents of different polarity and found out that the system phenoxathiin-thioxanthone presents a new emission band at longer wavelength than the D and A bands in non-polar solvents, which is quenched in polar ones. In order to explain the exciplex formation, which is determined by an electron transfer process, the standard free enthalpy for the latter was calculated according to the Rehm-Weller equation. The equilibrium constants and the activation barrier for the exciplex formation were determined as well from steady-state emission data at different donor concentrations and at different temperatures, respectively.

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Electrochemical polymerization of 9-cyanophenanthrene and characterization of its polymer

Xie

Jiang

et al. 2009

Synthetic Metals

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Temperature effect on the competition between the processes of 9-cyanophenanthrene exciplex decay

Cited by 3 publications

References 24 publications

The Behavior of Exciplex Decay Processes and Interplay of Radiationless Transition and Preliminary Reorganization Mechanisms of Electron Transfer in Loose and Tight Pairs of Reactants

The Behavior of Exciplex Decay Processes and Interplay of Radiationless Transition and Preliminary Reorganization Mechanisms of Electron Transfer in Loose and Tight Pairs of Reactants

Exciplex formation in the phenoxathiin-thioxanthone system

Electrochemical polymerization of 9-cyanophenanthrene and characterization of its polymer

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