Paper
Journal of Materials Chemistry A
improved two-photon absorption and sensing properties.
Finally, to conrm the nature of the nonlinear absorption of
negatively charged species (Ar–DPP–Nꢁ–Ar), the 2PEF spectra of
mDPP-Cl with 6 equiv. of TBAF are recorded under a constant
excitation wavelength (720 nm) with different input laser
powers (80–200 mW) (Fig. 6b). The gradually increased output
uorescence signal intensity with the input laser power affords
a power-law dependence of exponent 1.96 (the inset in Fig. 6b).
This square dependence underlines the occurrence of a two-
photon excitation process.
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3 Conclusions
Three N-monoalkylated diketopyrrolopyrrole (mDPP) deriva-
tives, 3,6-bis(4-bromo-/chloro-/methyl-phenyl)-2-octyl-pyrrolo-
[3,4-c]-pyrrole-1,4(2H,5H)-diones (named mDPP-Br/mDPP-Cl/
mDPP-Me), were synthesized from the commercially available
or easy-prepared corresponding DPP derivatives and their one-
and two-photon absorption and emission properties were
investigated in the absence and presence of TBAF. Proton NMR
titrations indicate that the addition of TBAF can induce the
intermolecular proton transfer (IPT) between the hydrogen
atom on the lactam N and the uoride anion. Moreover, the
electronically neutral (Ar–DPP–NH–Ar) and negatively charged
(Ar–DPP–Nꢁ–Ar) species are all highly uorescent (F ¼ 0.32–
0.61) and two-photon active (maximal d is 108 GM without TBAF
and 89 GM with TBAF), and the emission bands of negatively
charged species are signicantly red shied relative to those of
electronically neutral species. It is also observed that the
emission bands of electronically neutral species are gradually
decreased and those of negatively charged species are gradually
increased with the addition of TBAF, which can be used as the
ratiometric and uorometric sensors for uoride ions. Inspec-
tion of the one- and two-photon sensing properties reveals that
these mDPP derivatives have high detection sensitivity to uo-
ride anions upon two-photon excitation, probably due to that
the different excitation modes might involve different types of
excited states among these mDPP derivatives, mDPP-Br and
mDPP-Cl show better detection sensitivity to uoride anions
than mDPP-Me, implying that the substituent nature at the
benzene rings of DPP could affect the two-photon absorption
and sensing properties of mDPP derivatives. It is possible to
further improve the molecular optical properties by a subtle
manipulation of the substituent at the benzene ring of DPP
derivatives, and which is underway in our laboratory.
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Acknowledgements
We thank the NSFC of China (no. 51173092, 51073083), NSF of
Shandong Province (no. ZR2010EM023, ZR2012EMQ003), and
Open Project of State Key Laboratory of Supramolecular Struc-
ture and Materials (no. SKLSSM201207), Jilin University.
Notes and references
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