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Con clu sion
Bismaleimides and bisitaconimides having electron-
donating diphenylmethylamine, triphenylamine, or 2,5-
diphenyl-1,3,4-oxadiazole chromophore (A())-D(/)-A())
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)
as well as their saturated model compounds were
synthesized. These A())-D(/)-A()) monomers generally
display a strong intramolecular fluorescence quenching.
Their fluorescence quantum yields and lifetimes are
always lower than those of their corresponding satu-
rated compounds. The electron-poor CdC bond of ma-
leimide and itaconimide units (A())) plays a key role in
the intramolecular quenching, which is correlated to the
electron-accepting strength of A()) and the geometry
arrangement between A()) and D(/). Furthermore, the
absorption and emission of the charge-transfer complex
were observed for BIPA, which revealed that the in-
tramolecular quenching was attributed to an intramo-
lecular charge-transfer interaction. The intramolecular
charge-transfer mechanism is further confirmed by
time-resolved fluorescence spectroscopy. An intermo-
lecular fluorescence quenching study shows that the
intramolecular quenching is a distinct mechanism from
intermolecular interaction. On the basis of the strong
intramolecular quenching of A())-D(/)-A()) bismaleim-
ides, a new fluorescence approach can be developed to
monitor the process of polymerization and curing of
bismaleimides, which can be employed not only by an
intrinsic fluorescence technique but also by an extrinsic
fluorescence technique. The advantage of the new
fluorescence approach is that it provides information on
the chemical structure of CdC bond, which is unavail-
able from the currently applied environment-sensitive
fluorescence probe technique.
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Ack n ow led gm en t. Financial support from the Na-
tional Natural Science Foundation of China (No.5000-
3001) and the Research Fund for the Doctoral Program
of Higher Education (No 99000131) is gratefully ac-
knowledged.
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Su p p or tin g In for m a tion Ava ila ble: Text and a scheme
giving the synthetic procedures and spectral confirmations for
BSMA, BSPA BIPA, p-BMPO, p-BSPO, p-BIPO, m-BMPO,
m-BSPO, and m-BIPO, a figure showing Stern-Volmer plots
for the fluorescence quenching of BSPA, BSMA, and p-BIPO
by maleic anhydride and itaconic anhydride, and a figure
showing 1H NMR spectra during the model reaction of BMMA
with isobutylamine. This material is available free of charge
(13) Fluorescence quantum yields were calculated from the inte-
grated intensity under the emission band (A) using the
following equation: φ ) φr (A/Ar)(ODr/OD)(n2/nr2), where OD
is the optical density of the solution at the excitation
wavelength, and n is the refractive index. The optical density
of the solution for the calculation of quantum yields was less
than 0.1 at the excitation wavelength. The solvent 9,10-
diphenylanthrene in cyclohexane was used as reference
(φr ) 0.90) (Eaton, D. F. Pure. Appl. Chem. 1988, 60, 1107-
1114).
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