Resonance Raman spectroelectrochemistry. 6. Ultraviolet laser excitation of the tetracyanoquinodimethane dianion

Duyne, Richard P. Van; Suchanski, Mary R.; Lakovits, Joseph M.; Siedle, A. R.; Parks, K. D.; Cotton, Therese M.

doi:10.1021/ja00505a004

Cited by 42 publications

(9 citation statements)

References 9 publications

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“…Van Duyne and co-workers have shown, for example, that the frequencies of several Raman-active modes in TCNQ2"/"/0 (TCNQ = tetracyanoquinodimethane) shift linearly (incrementally) with formal oxidation state. 24 They have further shown, with TTF-TCNQ and related charge-transfer salts, that these shifts are also accurate predictors of fractional oxidation states.25…”

Section: Discussionmentioning

confidence: 98%

Electrochemical and spectral probes of metal/ligand orbital mixing in tetraammine(bipyridine)ruthenium(2+) and tetrammine(phenanthroline)ruthenium(2+)

Mines¹,

Roberts²,

Hupp³

1992

Inorg. Chem.

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Section: Discussionmentioning

confidence: 98%

Electrochemical and spectral probes of metal/ligand orbital mixing in tetraammine(bipyridine)ruthenium(2+) and tetrammine(phenanthroline)ruthenium(2+)

Mines¹,

Roberts²,

Hupp³

1992

Inorg. Chem.

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“…Other aspects of the cell design were identical with those described previously. 37 Electronics and Data Collection. The potentiostat, computer hardware, and programming used in performing CV and CDPV have been described.…”

Section: Methodsmentioning

confidence: 99%

An electrochemical investigation of the redox properties of bacteriochlorophyll and bacteriopheophytin in aprotic solvents

Cotton¹,

Duyne²

1979

J. Am. Chem. Soc.

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Knowledge of solvent effects on the redox properties of bacteriochlorophyll (BChl) and bacteriopheophytin (BPhco) is important for understanding their possible role(s) as intermediate electron acceptors in the primary photochemistry of photosynthetic bacteria. In the present study, an investigation of the electrochemical behavior of these compounds by cyclic voltammetry (CV) and cyclic differential pulse voltammetry (CDPV) in several aprotic solvents has shown that BChl aggregation and ligation interactions have a significant effect on its redox potentials. In methylene chloride, the one-electron reduction potential of BChl was found to shift positively by 200 mV to a value nearly identical with that of BPheo in the same solvent. The shift is most readily explained by the presence of BChl aggregates in this solvent. The one-electron oxidation potential is relatively unaffected by aggregation. In contrast, the formation of six-coordinate BChl in tetrahydrofuran (two molecules of solvent coordinated to the Mg atom of BChl) affects both the one-electron reduction and one-electron oxidation potential, with the greatest effect on the latter. Solvent effects on the redox properties of BPheo were found to be much smaller, a finding consistent with its inability to undergo aggregation and coordination interactions similar to those of BChl.During the past decade, considerable progress has been made toward understanding the primary photochemical events in photosynthetic bacteria.2 The reaction center (RC) complex has been purified3 and found to contain four bacteriochlorophyll (BChl) and two bacteriopheophytin (BPheo) molecules in addition to one quinone and three polypeptides. (See recent reviews in ref 4-8.) Two of the BChl molecules, the special pair, which absorb a t 870 nm (P870) are now generally accepted as the primary electron donor in photoinduced charge separ a t i~n .~-'~ The quinone molecule has been shown to act as the primary electron a c~e p t o r '~, '~ as defined on a millisecond time scale.I5 However, with the advent of picosecond (ps) absorption spectroscopy techniques, an intermediate electron acceptor with a lifetime of 250 ps has been d e t e~t e d . '~. ' 'The intermediate was identified by Fajer and co-workers18 as one of the BPheo molecules present in the R C by a comparison of the optical properties of the intermediate with those of the BPheo anion radical prepared electrochemically in methylene chloride. Subsequently, BPheo has been identified as the intermediate electron acceptor in a variety of photosynthetic bacterialThe picosecond data have recently been r e v i e~e d ,~~.~~ and possible artifacts of the method have been d i s c u~s e d .~~~~~Although the role of the remaining two BChl molecules and the BPheo molecule in the charge separation process has not been unambiguously demonstrated, there are some experimental observations that suggest BChl (PSOO) may be involved in some manner in the transfer of an electron from P870 to PBheo. These observations include the picosecond absorption stud...

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“…Investigators since the 1950's have been interested in CT complexes like tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) and HMB-TCNE and their analogues because of their interesting spectroscopic properties, 3 including time-resolved Raman spectroscopy, [4][5][6] and for their potential use as molecular metals. 7 For example, Miller and coworkers have done extensive work on ferromagnetic TCNE salts [8][9][10][11] while others have investigated conductive properties of TCNE and TCNQ compounds.…”

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confidence: 99%

Infrared spectroscopic determination of the degree of charge transfer in complexes of TCNE with methyl-substituted benzenes

2005

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Resonance Raman spectroelectrochemistry. 6. Ultraviolet laser excitation of the tetracyanoquinodimethane dianion

Cited by 42 publications

References 9 publications

Electrochemical and spectral probes of metal/ligand orbital mixing in tetraammine(bipyridine)ruthenium(2+) and tetrammine(phenanthroline)ruthenium(2+)

Electrochemical and spectral probes of metal/ligand orbital mixing in tetraammine(bipyridine)ruthenium(2+) and tetrammine(phenanthroline)ruthenium(2+)

An electrochemical investigation of the redox properties of bacteriochlorophyll and bacteriopheophytin in aprotic solvents

Infrared spectroscopic determination of the degree of charge transfer in complexes of TCNE with methyl-substituted benzenes

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