Synthesis and two-photon properties of new perylene bisimide derivatives

Article abstract of DOI:10.1246/cl.2006.1416

The synthesis of some novel perylene bisimide derivatives was reported and their linear absorption, emission, and two-photon properties were measured and discussed. Two-photon cross-sections for these compounds were determined to be 8735 GM maximum (nonli

Full text of DOI:10.1246/cl.2006.1416

1416
Chemistry Letters Vol.35, No.12 (2006)
Synthesis and Two-photon Properties of New Perylene Bisimide Derivatives
Bo Gao,1 Changgui Lu,2 Jin Xu,2 Fanshun Meng,1 Yiping Cui,ꢀ2 and He Tianꢀ1
1Labs for Advanced Materials and Institute of Fine Chemicals,
East China University of Science & Technology, Shanghai 200237, P. R. China
2Advanced Photonics Centre, Southeast University, Nanjing 210096, P. R. China
(Received September 27, 2006; CL-061126; E-mail: tianhe@ecust.edu.cn; cyp@seu.edu.cn)
The synthesis of some novel perylene bisimide derivatives
is its inherent low solubility. To overcome this problem, we
introduced 4-methylphenol in the bay region of perylene tetra-
carboxylic bisimides according to the literatures.4 Reaction of
N-butyl-1,6,7,12-tetrakis(4-methylpheoxy)-3,4:9,10-perylene
tetracarboxylic bisimide with 2-propynyl bromide and sodium
hydride in DMF afforded the target compound PBI in 60% yield.
Compound TPB-PBI and TPB-PBI2 were synthesized by the
Sonogashira coupling reaction of PBI with 1,3,5-tris(4-bromo-
phenyl)benzene. The reactions were carried out in triethyl-
was reported and their linear absorption, emission, and two-
photon properties were measured and discussed. Two-photon
cross-sections for these compounds were determined to be
8735 GM maximum (nonlinear transmittance, ꢁ7 ns, 10 Hz
and 850 nm). The frequency upconversion fluorescence was
observed under the excitation of 850-nm-nanoseconds laser
pulses with the peaks located around 669 nm.
.
amine/DMF mixture for 6 h under the catalyst of Pd2(dba)3
CHCl3.5 The final products were purified by chromatography
(silica gel) in yield of 20 and 13%, respectively. Other attempts
(including Pd(PPh3)4 or Pd(PPh3)2Cl2 with CuI in triethylamine)
gave either considerable amounts of monomer PBI or dimer
PBI2 as products.6 Compound PBI2 prepared from PBI in
triethylamine/THF mixture and catalyzed by Pd(PPh3)2Cl2/
CuI under dry air gave the yield of 60%. All compounds were
Intense research efforts have been geared toward the synthe-
sis of novel compounds with large two-photon absorption (TPA)
cross-sections due to their potential applications in three-dimen-
sional optical storage, two-photon optical power limiting and
two-photon upconverted lasing.1 Perylene and its derivatives
are photochemically and thermally stable. They have been
widely used as optical and electronic materials.2 However, the
two-photon properties of perylene were scarcely investigated;
only very recently several perylene tetracarboxylic derivatives
with large TPA cross-sections were reported by Mendoncꢀa and
co-workers.3
In this letter, we design and synthesize a series of novel
perylene bisimide derivatives by Sonogashira coupling reaction,
which have good solubility and attractive optical properties. The
molecular structures for these compounds are shown in Figure 1.
Perylene tetracarboxylic bisimides are good chromophores
with high fluorescence quantum yield. However, the drawback
1
characterized by H NMR and mass spectra.7
The linear optical properties of PBI, TPB-PBI, TPB-PBI2,
and PBI2 were studied in CH2Cl2 and the data are listed in
Table 1. As shown in Figure 2, all compounds show absorption
maximum around 573 nm and emission maximum around
603 nm with a shoulder emission at 650 nm; this shows the neg-
ligible effect of the different imide substituents on the absorption
and emission properties of the perylene bisimide chromophore
because of the nodes of the HOMO and LUMO orbital at the
imide nitrogen. Therefore, perylene bisimides can be regarded
as a closed chromophoric system with an S0–S1 transition
(polarized along the extended molecular axis) whose intensity
and position remain unaltered by the respective imide substitu-
ents.8
Br
C4H9
C4H9
O
N
O
O
N
O
Br
C4H9
TPA cross-sections for these compounds in CH2Cl2 were
determined by nonlinear transmittance method with ꢁ7 ns,
10 Hz and 850-nm-nanoseconds laser pulses.7 The concentration
R
R
R
R
R
R
R
R
O
O
O
O
O
O
O
O
O
O
N
O
R
R
R
O
O
O
O
O
N
O
O
N
O
R
O
R
N
1.0
0.8
0.6
0.4
0.2
0.0
1.0
0.8
0.6
0.4
0.2
0.0
O
PBI
O
TPB-PBI
TPB-PBI2
PBI2
N
O
R O
OR
O
O
R
PBI
N
C4H9
O
TPB-PBI
Br
R
R
R
R
TPB-PBI2
OO
OO
O
O
O
O
N
O
N C4H9
C4H9 N
O
N
O
O
R =
400
450
500
550
600
650
700
750
O O
OO
CH3
PBI2
R
R
Wavelength/nm
R
R
Figure 1. The chemical structures of PBI, TPB-PBI, TPB-
PBI2, and PBI2.
Figure 2. Normalized absorption and fluorescence spectra of
PBI, TPB-PBI, TPB-PBI2, and PBI2 in CH2Cl2.
Copyright Ó 2006 The Chemical Society of Japan

Chemistry Letters Vol.35, No.12 (2006)
Table 1. The optical properties of PBI, TPB-PBI, TPB-PBI2, and PBI2
1417
OPA
OPF
b
c
ꢁabs
"
ꢁem
ꢂ
ꢃ2
/GM
ꢁTPF
/nm
Compound
ꢀa
/nm
(104 mol Lꢂ1 cmꢂ1
)
/nm
cmꢃGWꢂ1
PBI
572
572
572
574
4.5
3.8
4.1
6.1
602
603
603
605
0.89
0.81
0.74
0.70
0.4
0.5
0.45
0.6
3106
3882
8735
4659
669
—
660
669
TPA-PBI
TPA-PBI2
PBI2
aFluorescence quantum yield determined using N,N-dibutyl-1,6,7,12-tetrachloro-3,4:9,10-tetracarboxylic bisimide as the standard.8
(ꢀ ¼ 92% in CHCl3). bTPA cross sections in CH2Cl2 measured at 850 nm (ꢁ7 ns). cTPF in CH2Cl2 excited by 850-nm-nanoseconds
laser pulses, C ¼ 0:005 M for PBI and PBI2, 0.002 M for TPB-PBI2, ꢁ1-mm propagation.
References and Notes
for TPA measurements was fixed at 0.005 M (0.002 M for
compound TPB-PBI2) in CH2Cl2. Typical TPA optical power
limiting curve at 850 nm (taking TPB-PBI2 for example) is
included in Figure 3. TPA cross-sections values, ꢀ (given in
GM = 10ꢂ50 cm4 s photonꢂ1 moleculeꢂ1) for compound PBI,
TPB-PBI, TPB-PBI2, and PBI2 were measured to be 3106,
3882, 8735, and 4659 GM, respectively. The large values of
TPA cross-sections are probably affected by excited state
absorption (ESA) as ‘‘effective’’ TPA cross-sections.9 Owing
to the multi-branched structure, TPA cross-section of TPB-
PBI2 is larger than that of PBI and TPB-PBI. Compound PBI2
has larger TPA cross-section compared to PBI, may result from
the slightly increasing conjugated system which is due to the
acetylenic homo-coupling.
A red fluorescence emission could be observed from a sam-
ple solution excited by 850-nm-nanosecond laser pulses through
2-PA process. The frequencies of the upconversion fluorescence
emission peak are listed in Table 1. All of the emission peaks get
slightly red shift because of the strong re-absorption effect in
the short wavelength range of the emission band, when the
fluorescence beams propagate through such highly concentrated
sample medium.
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In summary, a series of novel perylene bisimide derivatives
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physical properties were studied. These compounds have
relatively large two-photon absorption cross-sections, which
have potentials for application as novel TPA materials with high
photostability, thermal stability, and fluorescence quantum
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The detailed synthesis of the compounds and the measurement
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which is available electronically on the CSJ-Journal Website
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.5
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2.5
3.0
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.
Input Intensity (GW cm )
Figure 3. Measured output intensity versus input intensity of
the 850-nm laser pulses of compound TPB-PBI2.
Published on the web (Advance View) November 11, 2006; doi:10.1246/cl.2006.1416