TY - JOUR
T1 - A (π-extended tetrathiafulvalene)-fluorene conjugate. Unusual electrochemistry and charge transfer properties
T2 - The first observation of a covalent D2+-σ-A.- Redox state
AU - Perepichka, Dmitrii F.
AU - Bryce, Martin R.
AU - Perepichka, Igor F.
AU - Lyubchik, Svetlana B.
AU - Christensen, Christian A.
AU - Godbert, Nicolas
AU - Batsanov, Andrei S.
AU - Levillain, Eric
AU - McInnes, Eric J.L.
AU - Zhao, Jing P.
PY - 2002/11/27
Y1 - 2002/11/27
N2 - The synthesis of novel electrochemically amphoteric TTFAQ-σ-A compounds (TTFAQ = 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene, σ = saturated spacer, A = polynitrofluorene acceptor) is reported. Their solution redox behavior is characterized by three single-electron reduction and one two-electron oxidation waves. Electrochemical quasireversibility of the TTFAQ2+ state and a low Eox - Erec gap (≈0.25 V) for 3-(9-dicyanomethylene-4,5,7-trinitrofluorene-2-sulfonyl)-propionic acid 2-[10-(4,5-dimethyl-[1,3]dithiol-2-ylidene)-9, 10-dihydroanthracen-9-ylidene]-5-methyl-[1,3]dithiol-4-ylmethyl ester (10) has enabled the electrochemical generation of the hitherto unknown transient D2+-≠-A.- state as observed in cyclic voltammetry and time-resolved spectroelectrochemistry. The ground state of compound 10 was shown to be ionic in the solid but is essentially neutral in solution (according to electron paramagnetic resonance). The X-ray structure of an intermolecular 1:2 complex between 2-[2,7-bis(2-hydroxyethoxy)-9,10-bis(4,5-dimethyl-[1,3] dithiol-2-ylidene)-9,10-dihydroanthracene and 2,5,7-trinitro-4-bromo-9-dicyanomethylenefluorene, 14·(17)2, reveals, for the first time, full electron transfer in a fluorene charge-transfer complex.
AB - The synthesis of novel electrochemically amphoteric TTFAQ-σ-A compounds (TTFAQ = 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene, σ = saturated spacer, A = polynitrofluorene acceptor) is reported. Their solution redox behavior is characterized by three single-electron reduction and one two-electron oxidation waves. Electrochemical quasireversibility of the TTFAQ2+ state and a low Eox - Erec gap (≈0.25 V) for 3-(9-dicyanomethylene-4,5,7-trinitrofluorene-2-sulfonyl)-propionic acid 2-[10-(4,5-dimethyl-[1,3]dithiol-2-ylidene)-9, 10-dihydroanthracen-9-ylidene]-5-methyl-[1,3]dithiol-4-ylmethyl ester (10) has enabled the electrochemical generation of the hitherto unknown transient D2+-≠-A.- state as observed in cyclic voltammetry and time-resolved spectroelectrochemistry. The ground state of compound 10 was shown to be ionic in the solid but is essentially neutral in solution (according to electron paramagnetic resonance). The X-ray structure of an intermolecular 1:2 complex between 2-[2,7-bis(2-hydroxyethoxy)-9,10-bis(4,5-dimethyl-[1,3] dithiol-2-ylidene)-9,10-dihydroanthracene and 2,5,7-trinitro-4-bromo-9-dicyanomethylenefluorene, 14·(17)2, reveals, for the first time, full electron transfer in a fluorene charge-transfer complex.
UR - http://www.scopus.com/inward/record.url?scp=0037184485&partnerID=8YFLogxK
U2 - 10.1021/ja012518o
DO - 10.1021/ja012518o
M3 - Article
C2 - 12440922
AN - SCOPUS:0037184485
SN - 0002-7863
VL - 124
SP - 14227
EP - 14238
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 47
ER -