Heterocyclic Molecule with Two-Photon Induced Blue Fluorescence
51
Table 1. Photophysical properties of molecule 3 in chloroform compared to literature data of
two-photon induced blue emissive fluorophores reportedA
spf
max
tpf
abs
Molecules
λ
[nm]
λ
[nm]
Φf [%]
λ
[nm]
max
σ2 [GM]B
max
3
395
359
384
463
454
486
51
38
61
480
470
487
239
180
118
ASBM[8]
CSSB[7]
spf
, λ , λtpf : peak wavelengths in the linear absorption, one-photon excited fluorescence and
A
abs
λ
max max
max
two-photon excited fluorescence spectra, respectively.
B1 GM = 10−50 cm4 s photon−1
.
Experimental
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200300272
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1H NMR spectra were recorded in CDCl3 on a FT-NMR spectrome-
ter (Varian Mercury VX300) operating at 298 K. Chemical shifts were
recorded in parts per million (ppm) relative to tetramethylsilane (TMS).
Elemental analysis was performed using a elemental analyzer (Carlo–
Erba model 1106). Column chromatography was carried out on silica
gel zcx-α (200–300 mesh). All chemicals are commercially available
and were used as-received unless stated otherwise. The intermediates 1
and 2 were synthesized according to reported methods[27,28] with minor
modification. The title compound 3 was prepared by the Wittig–Horner
reaction by the following procedure.
N-Hexadecylcarbazole-3-carbaldehyde (168 mg, 0.4 mmol), the
intermediate 2 (104 mg, 0.2 mmol), and catalyst 18-crown-6 were dis-
solved in anhydrous dichloromethane (50 mL), and then ButOK powder
(67 mg, 0.6 mmol) was added in portions under a nitrogen atmosphere.
The reaction mixture was stirred at room temperature overnight. Then
the mixture was poured into water (20 mL), extracted with chloroform
(30 mL ×3), dried with sodium sulfate, and concentrated. Purification
was performed by column chromatography with chloroform as eluent.
Furtherpurificationbyrecrystallizationinethanol/chloroformgavepure
products as pale yellow needles (40 mg, 38%) (Found: C 84.3, H 8.7, N
4.8. Calc for C74H92N4O: C 84.4, H 8.8, N 5.3%). δH (CDCl3) 0.88 (t,
6H, CH3), 1.25–1.35 (m, 52H, CH2), 1.88 (m, 4H, CH2), 4.32 (t, 4H,
NCH2), 7.20 (d, J 16.2, 2H, CH=CH), 7.26–7.30 (br, 2H, CH=CH),
7.41–7.50 (m, 8H, ArH), 7.72 (d, J 8.4, 6H, ArH), 8.16 (d, J 8.4, 6H,
ArH), 8.28 (s, 2H, ArH).
UV-vis absorption spectra were recorded on a Hitachi U-3010 UV-
vis spectrophotometer. Photoluminescent spectra were recorded on a
Shimadzu RF-5301 fluorescence spectrophotometer.
The experimental set-up for the TPIF and TPA cross section σ2
measurements was similar to that described by Oulianov et al.[29] The
excitation source for the TPIF spectra and σ2 measurement was a laser
system (Mira 900) at 150 fs emission, 788 nm pulses at 76 MHz repeti-
tion rate. The TPIF spectrum was recorded in a direction perpendicular
to the pump beam by an CCD-array spectrometer (Acton Spectrapro
2500I). The intensity of the incident beam was monitored by the detec-
tor of a power meter (Coherent, FieldMaster). The beam was focused
by an f = 150 mm lens into the solution of the sample and was close
to the TPIF-collection wall of the cell (10 mm × 10 mm) to minimize
the re-absorption effect. The TPIF intensity was obtained by integrating
over the entire emission range of TPIF spectrum.
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3765(20020902)8:17<3907::AID-CHEM3907>3.0.CO;2-F
[14] R. Kannan, G. S. He, T.-C. Lin, P. N. Prasad, R.A. Vaia, L.-S. Tan,
Chem. Mater. 2004, 16, 185. doi:10.1021/CM034358G
[15] O.-K. Kim, K.-S. Lee, H. Y. Woo, K.-S. Kim, G. S. He,
J. Swiatkiewicz, P. N. Prasad, Chem. Mater. 2000, 12, 284.
doi:10.1021/CM990662R
[16] Y.-Y. Chien, K.-T. Wong, P.-T. Chou, Y.-M. Cheng, Chem.
Commun. 2002, 2874. doi:10.1039/B208269A
[17] N. C. Yang, J. K. Jeong, D. H. Suh, Chem. Lett. (Jpn.) 2003, 32,
40. doi:10.1246/CL.2003.40
Acknowledgments
[18] M. R. Robinson, M. B. O’Regan, G. C. Bazan, Chem. Commun.
2000, 1645. doi:10.1039/B004739M
[19] N. D. McClenaghan, R. Passalacqua, F. Loiseau, S. Campagna,
B.Verheyde,A. Hameurlaine,W. Dehaen, J.Am. Chem. Soc. 2003,
125, 5356. doi:10.1021/JA021373Y
This work was supported by the National Natural Science
Foundation of China (grants no. 90201002 and 10474075).
[20] S.-J. Chung, K.-S. Kim, T.-C. Lin, G. S. He, J. Swiatkiewicz,
P. N. Prasad, J. Phys. Chem. B 1999, 103, 10741. doi:10.1021/
JP992846Z
[21] T.-C. Lin, G. S. He, P. N. Prasad, L.-S. Tan, J. Mater. Chem. 2004,
14, 982. doi:10.1039/B313185H
[22] M. Halik, W. Wenseleers, C. Grasso, F. Stellacci, E. Zojer,
S. Barlow, J.-L. Brédas, J.W. Perry, S. R. Marder, Chem. Commun.
2003, 1490. doi:10.1039/B303135G
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