J . Org. Chem. 2001, 66, 3397-3401
3397
In tr a m olecu la r Ch a r ge-Tr a n sfer In ter a ction in a New Dya d Ba sed
on C60 a n d Bis(4′-ter t-bu tylbip h en yl-4-yl)a n ilin e (BBA) Don or
Toshinobu Ohno,* Kazuyuki Moriwaki, and Toshiyuki Miyata
Osaka Municipal Technical Research Institute, 1-6-50 Morinomiya, J oto-ku, Osaka 536-8553, J apan
ohno@omtri.city.osaka.jp
Received J uly 20, 2000 (Revised Manuscript Received February 6, 2001 )
A novel dyad 2 based on C60 and bis(4′-tert-butylbiphenyl-4-yl)aniline (BBA) donor has been
synthesized and characterized. Cyclic voltammetry (CV) and UV-vis spectra of 2, 61-phenyl-1,
2-methanofullerene[60] 4, 1,2-methanofullerene[60] 5, and BBA were measured and analyzed. CV
measurements showed that a reversible oxidation wave of 2 was positively shifted by 40 mV
compared to that of BBA. More remarkably, comparing UV-vis spectra of 2 and 5 shows the big
hyperchromic effect of 2 on a broad band at 500 nm despite lacking of more than 400 nm of
absorbance for BBA. These results indicate obvious evidence of intramolecular charge-transfer
interactions between C60-moiety and BBA.
In tr od u ction
On the other hand triarylamines are one of strong
electron donor moieties and an important class of com-
pounds because they form stable aminium radical cations
and can be building blocks for high-spin polyradical and
conducting polymers as well as the hole-transport layer
in electroluminescent devices.5 In recent years, Shirota
et al. reported that tris(oligophenylenyl)amine deriva-
tives as well as a novel class of starburst molecules
consisting of a fully conjugated π-electron system like
4,4′,4′′-tris(diphenylamino)triphenylamine have become
a new type of low-molecular weight materials that can
form stable amorphous glasses, which are attractive for
their excellent processability, flexibility, transparency,
absence of grain boundaries, and isotropic properties.6
Buckminsterfullerene C60 and its derivatives exhibit
a number of distinctive electronic and photophysical
properties and have been investigated for the applica-
tion as novel molecular electronic devices.1,2 In one of the
most attractive strategies, various electron donors have
been covalently linked to the C60 cage by different
synthetic procedures to attain efficient intramolecular
energy and electron transfer and to generate long-lived
charge-separated states in these C60-donor dyads with
the intention of developing artificial photosynthetic
systems.1,3 C60 is expected to be a potential electron
acceptor in artificial photosynthesis because of sym-
metrical shape, large size, and properties of its π-electron
system.4
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10.1021/jo001100q CCC: $20.00 © 2001 American Chemical Society
Published on Web 04/17/2001