Solid supramolecular architecture of a perylene diimide derivative for fluorescent enhancement

Article abstract of DOI:10.1002/asia.201200659

A new p-phenylenevinylene-linked perylene diimide has been synthesized and self-assembled for the formation of zero-dimensional molecular aggregate structures of nanospheres and vesicles through solvent tuning. The solid-state optical properties induced by a special wavelength laser were studied and the results indicated excellent fluorescent enhancement properties. The emission intensity of these aggregates increased with elongation of the laser irradiation time. Based on the analysis of variable-temperature ¹H NMR spectra, DFT calculations, and the single-crystal structure of the linkage group, a conformation-dependent fluorescent enhancement mechanism could be demonstrated. The mechanism is different from the fluorescent bleaching of normal solid-state fluorescent materials and offers potential applications in optical devices. Flash! A novel p-phenylenevinylene-linked perylene diimide has been synthesized and utilized to self-assemble into zero-dimensional molecular aggregate structures of nanospheres and vesicles. The solid-state optical properties induced by the special wavelength laser indicated excellent fluorescent enhancement properties and increased emission intensity of these aggregates prolonged laser irradiation. Copyright

Full text of DOI:10.1002/asia.201200659

FULL PAPER
DOI: 10.1002/asia.201200659
Solid Supramolecular Architecture of a Perylene Diimide Derivative for
Fluorescent Enhancement
Yanwen Yu,[a, b] Qinghua Shi,[a] Yongjun Li,*[a] Taifeng Liu,[a, b] Liang Zhang,[a, b]
Zhigang Shuai,[a] and Yuliang Li*[a]
Abstract: A new p-phenylenevinylene-
linked perylene diimide has been syn-
thesized and self-assembled for the for-
mation of zero-dimensional molecular
aggregate structures of nanospheres
and vesicles through solvent tuning.
The solid-state optical properties in-
duced by a special wavelength laser
were studied and the results indicated
excellent fluorescent enhancement
properties. The emission intensity of
these aggregates increased with elonga-
tion of the laser irradiation time. Based
on the analysis of variable-temperature
1H NMR spectra, DFT calculations,
and the single-crystal structure of the
linkage group, a conformation-depen-
dent fluorescent enhancement mecha-
nism could be demonstrated. The
mechanism is different from the fluo-
rescent bleaching of normal solid-state
fluorescent materials and offers poten-
tial applications in optical devices.
Keywords: conformation analysis ·
fluorescence · perylene diimides ·
self-assembly
Introduction
ties of p-conjugated compounds.[6a,9] The p–p interactions in
planar conjugated molecules can result in the quenching of
radiative processes in the solid state and low photolumines-
cence efficiency, owing to the formation of H aggregates in
the ground state and excimers in the excited state.[10] To
reduce H aggregation, one effective way is to design nonpla-
nar conjugated molecules to reduce p–p interactions of
planar conjugated molecules, such as the formation of cross
dipole stacking,[8g,11] the introduction of bulky substitu-
ents,[12] and encapsulation by clathrates.[13] Tuning the spec-
troscopic properties of p-conjugated polymers by controlling
the conformations obtained from interface self-assembly
was reported,[8f] but the optical properties of simple conju-
gated molecules, existing in the form of different conforma-
tions and spatial arrangements, have seldom been studied;
this is probably due to the lack of effective measurement
methods and difficulties in designing appropriate molecules.
Herein, we studied the fluorescent enhancement behavior of
a new p-phenylenevinylene-linked perylene diimide aggre-
gate induced by laser irradiation, and a conformation-de-
pendent mechanism was proposed based on variable-tem-
The field of luminescent solids has aroused much interest in
recent decades[1] for their applications in light-emitting
diodes[2] and field-effect transistors.[3] Many methods are
well developed for tuning of their optical and electronic
properties, such as photochemical isomerization by heat or
light,[4] self-assembly of organic ligands and inorganic metal
ions,[5] converting polymorphic materials reversibly from
one form to another by external stimuli.[6] Ordered molecu-
lar assemblies can have different properties from those of
their individual constituent molecules.[7] The photophysical
properties of p-conjugated compounds in the solid state
depend largely upon their molecular packing style, which
can be tuned by various noncovalent forces. For example,
the relative positions of adjacent molecules and directions
of their dipole moments can strongly influence lumines-
cence, exciton migration, and carrier mobility.[3a,8] Thus to
tune their properties, it is essential to understand the nature
of noncovalent forces that determine molecular packing in
the solid state and how they affect the photophysical proper-
1
perature H NMR spectra, DFT calculations, and the single-
crystal structure of the linkage group.
[a] Dr. Y. Yu, Dr. Q. Shi, Prof. Y. Li, Dr. T. Liu, Dr. L. Zhang,
Prof. Z. Shuai, Prof. Y. Li
Beijing National Laboratory for Molecular Sciences (BNLMS)
CAS Key Laboratory of Organic Solids, Institute of Chemistry
Chinese Academy of Sciences, Beijing 100190 (P.R. China)
Fax : (+86)10-82616576
Results and Discussion
The syntheses of compounds 7 and 8 from commercially
available compounds are illustrated in Scheme 1. Com-
pounds 3 and 4 were synthesized according to methods pro-
vided in the literature.[14] Compound 5 can be obtained in
78% yield by the Suzuki reaction and subsequent photocyc-
lization affords 6 in 100% yield. When using dry THF as the
solvent, in the presence of NaH, the reaction of 3 and 5 suc-
E-mail: liyj@iccas.ac.cn
ylli@iccas.ac.cn
[b] Dr. Y. Yu, Dr. T. Liu, Dr. L. Zhang
Graduate University of Chinese Academy of Sciences
Beijing 100049 (P.R. China)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201200659.
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Scheme 1. The synthetic scheme for the preparation of the compounds 7 and 8 and the molecular structures of compounds 9 and 10. [PdCl2ACHTNUTRGNEUNG(dppf)]: [1,1’-
bis(diphenylphosphino)ferrocene]dichloropalladium(II), THF: tetrahydrofuran, TBAB: tetrabutylammonium bromide.
cessfully affords compound 7, which is an amorphous solid,
in 5.4% yield after being stirred overnight at 508C. A mix-
ture of 3 and 6 can produce amorphous solid 8 in 9.7%
yield under the same conditions. Products were character-
1
ized by H and 13C NMR spectroscopy, MALDI-TOF MS,
and elemental analysis. Compound 7 is soluble in dichloro-
methane, CHCl3, THF, and 1,1,2,2-tetrachloroethane, and
microsoluble in acetone, acetonitrile, and methanol. Com-
pound 8 is soluble in CHCl3, THF, 1,1,2,2-tetrachloroethane,
but microsoluble in CH2Cl2 and acetone, and insoluble in
acetonitrile, methanol, N,N-dimethylformamide (DMF), di-
methylsulfoxide (DMSO), and toluene.
Absorption and emission spectra of these compounds in
CH2Cl2 at room temperature are shown in Figure 1 and
their photophysical properties are listed in Table 1. The per-
ylene core p–p* transition absorption bands (emax
=
25100mÀ1 cmÀ1 for 7, and emax =132900mÀ1 cmÀ1 for 8) ac-
companied by p-phenylenevinylene unit p–p* transition ab-
sorption bands can be clearly observed. Owing to steric hin-
drance, the p-phenylenevinylene moiety is nonplanar with
Abstract in Chinese:
Figure 1. a) Absorption and b) emission spectra of compounds 7, 8, 9,
and 10 in CH2Cl2 (2ꢁ10À5 m) at room temperature.
respect to the perylene ring (see Figure 5 below), and acts
as the electron donor in these compounds. As a result, the
maximum absorption value of 7 only has a small blueshift of
3 nm relative to that of the parent compound (the unsubsti-
tuted PDI; lmax =527 nm), and the maximum absorption
value of the p-phenylenevinylene unit only has a redshift of
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Table 1. Photophysical and electrochemical properties of the compounds 7, 8, 9, and 10.
[c]
Abs[a] lmax [nm]
e[a] [mÀ1 cmÀ1
]
Fluorescence[b] lmax [nm] Ffl
Eox (V vs. SCE)[d] Ered (V vs. SCE)[d] HOMO/LUMO [eV][g] Eg [eV]
PDI 527
79400
534
574
557, 522
590
447
1
1.72[e]
À0.57,[e] À0.77[e]
À0.61,[e] À0.83[e]
À0.71,[e] À0.90[e]
À0.58,[e] À0.79[e]
À6.05/À3.90
À5.37/À3.86
À5.49/À3.81
À6.16/À3.88
À5.39/
2.15
1.51
1.68
2.28
7
8
524, 492, 403, 335 25100
498, 463, 435, 319 132900
0.008 1.38,[f] 0.98[f]
0.004 1.44,[f] 1.11[f]
9
10
536, 502
391, 325
48700
45700
0.70
1.79[f]
1.29,[e] 0.95[e]
[a] Measured in CH2Cl2 (1.0ꢁ10À5 m). [b] Measured in CH2Cl2 (1.0ꢁ10À6 m), upon excitation at the absorption maximum. [c] In CH2Cl2, N,N’-di(2,6-diiso-
propylphenyl)perylene-3,4:9,10-tetracarboxylic acid diimide (the unsubstituted PDI, Ffl =1 in CHCl3)[15] as a standard. [d] Performed in CH2Cl2 with
nBu4NPF6 (0.05m) as the supporting electrolyte and a standard calomel electrode (SCE) as the reference electrode. [e] Half-wave potential. [f] Peak po-
tential. [g] HOMO and LUMO levels are obtained directly from the onset potentials measured by cyclic voltammetry, according to a method reported in
the literature.[16]
12 nm from 391 to 403 nm, thus indicating that the charac-
teristics in the absorption spectrum of compound 7 basically
remain as those of the PDI and 10. The cyclic phenyl group
extends the p core of perylene along the short molecular
axis; the absorption of 8 is blueshifted by 29 nm to 498 nm
with p-phenylenevinylene p–p* transition absorption bands
redshifted by 44 nm to 435 nm. The fluorescence quantum
yields of compounds 7 and 8 are less than 0.01 based on the
parent compound PDI as the standard (Ffl =1 in CHCl3), in-
dicating that they are practically nonfluorescent.
The measured redox potentials of 7 and 8 are listed in
Table 1 (see Figure S1 in the Supporting Information). Com-
pounds 7 and 8 both exhibit two irreversible one-electron
oxidation peaks at 0.98 and 1.38, and 1.11 and 1.44 V, re-
spectively. Compared with 9, the first oxidation potential
shifts negatively from 1.79 to 0.98 V for 7 and 1.11 V for 8;
this indicates that these molecules are much easier to oxi-
dize than 9. Compared with 10, the first oxidation potential
of 7 is positively shifted only by about 30 mV from 0.95 to
0.98 V, and that of 8 is positively shifted from 0.95 to 1.11 V
(160 mV), reflecting that 7 and 8 are more difficult to oxi-
dize than 10. Compounds 7 and 8 both show two reversible
reduction potentials. Compared with the reduction poten-
tials of 9 (À0.58 and À0.79 V vs. SCE), the half-wave reduc-
tion potentials versus SCE (n=0.1 VsÀ1) are À0.61 and
À0.83 V for 7, and À0.71 and À0.90 V for 8, respectively, in-
dicating that the reduction potentials of 7 and 8 both have
a significant negative shift.
absorbs between d=7.62 and 7.65 ppm; the signal is split
into two signals by magnetic moments of proton B. The four
hydrogen atoms D (4H) of the two benzene rings connected
with perylene give rise to a signal split by its adjacent hydro-
gen atom into two signals at d=7.60 and 7.62 ppm, which
partly overlap with the signal from proton C. From the rela-
tionship between the number of signals in the spectrum and
the number of different types of hydrogen atoms in the
compound, we can deduce that compound 7 is symmetric.
When considering the melting and boiling points of the deu-
terated solvent, CD2Cl2 and CDCl2CDCl2 were chosen for
the low (from 213 to 293 K) and high temperature (from
305 to 375 K) experiments, respectively (Figure 2b). With
decreasing temperature, the signals from protons A and B
both shift upfield (for example, the signal from the proton
A shifts upfield from d=7.21 ppm in the 293 K spectrum to
d=6.94 ppm in the 213 K spectrum), but the other signals
shift a little or remain the same, as indicated in Figure 2b.
The induced magnetic fields generated by the circulation of
delocalized p electrons can either shield or deshield nearby
protons. Whether a proton is shielded or deshielded and the
extent to which shielding or deshielding occurs mainly
depend on the location of the proton in the induced field.[17]
When the temperature is 293 K or higher, proton A is de-
shielded by both the middle benzene ring and the adjacent
vinylene group (Figure 2a and b). With decreasing tempera-
ture, proton A is not only deshielded, mainly by the two in-
tramolecular groups, but also gradually shielded weakly by
other nearby molecular benzene rings and vinylene groups,
resulting in the upfield shift. The situation for proton B is
The HOMO and LUMO energy levels of these com-
pounds and their energy gaps are also listed in Table 1. The
electronic structures of the perylene derivatives are signifi-
cantly different from that of the parent PDI. The p-elec-
tron-rich p-phenylenevinylene unit effectively extends the p-
conjugation system, raising the HOMO level and leaving
the LUMO level almost unchanged, thereby resulting in
a smaller energy gap and making the molecules much easier
to oxidize.
similar. Compound
7 retains a symmetrical structure
throughout the variable-temperature experimental processes
because no signal splitting in the signal from proton A (2H)
of the middle benzene ring, but the upfield shift was ob-
served. The aggregation style of 7 can be inferred as that de-
picted in Figure 2c and d from the above data. The adjacent
molecules of 7 aggregate through face to face p–p stacking
of the middle benzene ring as a center and there is an angle
of about 1018 between the two vinylenes (see Figure 6
below and Figure 2d).
The p–p-stacking interactions of 7 induced good zero-di-
mensional nanostructures. Compound 7 (1.0ꢁ10À4 m, 5 mL)
in CH2Cl2 was put onto a silicon substrate with simultaneous
addition of cyclohexane (5 mL): the combined system evapo-
Variable-temperature 1H NMR spectra of 7 (Figure 2b)
indicated the aggregation mode between adjacent molecules.
At 298 K, the singlet at d=7.22 ppm is assigned to proton A
(2H) of the middle benzene ring (Figure 2a). The signal
from proton B (2H) of the two vinylenes split by magnetic
moments of proton C into a 1:1 doublet occurs between d=
7.28 and 7.31 ppm, and proton C (2H) of the two vinylenes
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A Perylene Diimide Derivative
rates completely at room temperature and is then directly
used for the SEM study. Zero-dimensional nanovesicles with
diameters of about 300 nm are the main morphology (Fig-
ure 3a). However, in hexane, zero-dimensional nanospheres
with diameters of about 800 nm can be observed in the
SEM images (Figure 3c). The presence of these nanovesicles
Figure 3. SEM (a and c) and TEM images (b and d) of compound 7 pre-
pared in CH2Cl2/cyclohexane (1:1 v/v; a and b) or CH2Cl2/hexane (1:1 v/
v; c and d) mixtures at room temperature.
and nanospheres were further confirmed by TEM images
(Figure 3b and d). The morphological experiments clearly
demonstrate that the solvent effects influence the formation
of zero-dimensional nanostructures.
We further studied the optical properties of these nano-
particles with laser scanning confocal microscopy (LSCM)
and found that the emission intensity increased with elonga-
tion of laser irradiation time at 515 nm. The emission band
of nanospheres of 7 was observed by time-dependent fluo-
rescent spectra with laser irradiation at 515 nm (Figure 4d).
The nonfluorescent nanospheres of 7 showed an enhanced
emission centered at 599 nm. The experiments related to the
excitation showed that it was only the p–p* transition ab-
sorption bands of perylene that could excite this optical be-
havior. These results indicate that, after self-assembly, com-
pound 7 exhibits high selectivity to both light and wave-
length. We also observed the sample prepared under the
above-mentioned conditions without self-assembly because
a spin-coated sample did not show these optical phenomena.
In addition, other morphological self-assembled products,
such as microrods and nanovesicles obtained by different
self-assembly methods, can also exhibit the same phenom-
ena of fluorescence enhancement (see Figures S2 and S3 in
the Supporting Information). The MS spectrum (TOF) of
the sample after laser irradiation at 515 nm still only showed
a signal at m/z 1844 (see the Supporting Information); this
indicates the good chemical stability of 7 and indicates that
the emission enhancement is not due to the photocyclization
of 7 or the destruction of 7.
Figure 2. a) Room-temperature 1H NMR spectrum (600 MHz) of 7 in
CD2Cl2. b) Variable-temperature 1H NMR spectra of
7 recorded at
600 MHz in CD2Cl2 from 213 to 293 K and recorded at 300 MHz in
CDCl2CDCl2 from 305 to 375 K. Side (c) and top views (d) of the aggre-
gates of the most stable thermodynamic conformation of 7.
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Yongjun Li, Yuliang Li, et al.
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Figure 5. The most stable thermodynamic conformation of 7 obtained by
using DFT calculations at the B3LYP/6-31G level.
cessfully obtained the X-ray crystal structure of 10 (see Fig-
ure S5 in the Supporting Information). The X-ray crystal
structure indicates that the three benzene rings and two vi-
nylene groups are all coplanar; this is identical to the corre-
sponding part of the most stable thermodynamic conforma-
tion of 7 obtained by calculations (Figure 5). The control ex-
periments for compound 8 did not reveal the same emission
enhancement with laser irradiation. Based on the variable-
Figure 4. LSCM images after laser irradiation at 515 nm (a), time-depen-
dent intensity plot of the fluorescence emission (b and c), and time-de-
pendent emission spectra (d) of self-assembled spherical nanoparticles of
the compound 7. (A colored version of this figure is available in the Sup-
porting Information.)
1
To gain more insight into the abnormal photophysical
properties of compound 7 on the molecular level, calcula-
tions at the B3LYP/6-31G level obtained by using the Gaus-
sian 03 program[18] for the molecular conformation of 7 were
studied. The most stable thermodynamic conformation is de-
picted in Figure 5. The two perylene diimides are parallel,
forming a dihedral angle of 54.848 with the p-phenyleneviny-
lene unit. HOMO–LUMO analysis indicated that the elec-
tron density in the HOMO was mostly localized on the p-
phenylenevinylene moiety and the density in the LUMO
was mainly concentrated on the two PDI planes (see Fig-
ure S4 in the Supporting Information), thus reflecting that
electron transfer from the p-phenylenevinylene moiety to
the PDI planes resulted in the weak emission of PDI.
temperature H NMR spectra of 7 and these control experi-
ments, the mechanism for the phenomena could be pro-
posed. First, owing to steric hindrance between intermolecu-
lar 2,6-diisopropylphenyl groups, and van der Waals interac-
tions between intermolecular oxyalkyl chains, compound 7
aggregates as depicted in Figure 2c and d. There is an angle
of about 1018 between two adjacent intermolecular double
bonds with the face-to-face p–p stacked middle benzene
ring as a center, and this style is repeated every two adjacent
molecules (Figure 6). Second, under irradiation from the
laser (515 nm), the molecules obtain enough energy to over-
come the rotational energy barrier and rotate on its axis to
and fro at the balance position, that is, the molecules change
from one conformation to another. Because of steric hin-
drance from adjacent molecules in the self-assembled solid
state, the molecule rotates to the position at which the p-
To explain the phenomena induced by the special wave-
length laser reasonably, we synthesized 8 and 10 and suc-
Figure 6. Proposed mechanism for the fluorescence emission enhancement of 7 after self-assembly induced by the special wavelength laser.
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A Perylene Diimide Derivative
matography over silica gel, eluted with CH2Cl2, to afford 5 as a red solid
(159 mg, 78.0%). M.p. 2208C; 1H NMR (400 MHz, CDCl3): d=10.17 (s,
1H), 8.87–8.77 (m, 4H), 8.69 (s, 1H), 8.25 (d, J=8.2 Hz, 1H), 8.11 (d, J=
8.0 Hz, 2H), 7.91 (d, J=8.2 Hz, 1H), 7.80 (d, J=8.0 Hz, 2H), 7.56–7.46
(m, 2H), 7.37 (dd, J=10.2, 8.0 Hz, 4H), 2.84–2.72 (m, 4H), 1.22–
1.17 ppm (m, 24H); 13C NMR (100 MHz, CDCl3): d=191.49, 163.59,
163.56, 163.39, 163.31, 148.66, 145.73, 145.70, 140.42, 136.25, 135.92,
135.50, 134.88, 134.71, 133.41, 132.05, 131.99, 131.76, 130.67, 130.51,
129.89, 129.82, 129.80, 129.70, 129.39, 128.52, 127.92, 124.25, 124.21,
123.56, 123.45, 123.25, 122.84, 122.71, 29.36, 29.28, 24.12 ppm; IR (KBr):
n˜ =2965, 2930, 2870, 1705, 1668, 1593, 1461, 1404, 1341, 1252, 1201, 964,
816, 747, 669, 558 cmÀ1; HRMS (EI): m/z calcd for C55H46N2O5: 814.3407;
found: 814.3417.
phenylenevinylene part is almost perpendicular to both
sides of the perylene units and is stuck fast and frozen; this
decreases interactions between the donor (the p-phenylene-
vinylene unit) and acceptor (the perylene group), thereby
leading to the appearance of the emission of the J-stacked
perylene diimide itself.
Conclusion
A class of new p-phenylenevinylene-linked perylene dii-
mides have been synthesized and utilized to construct zero-
dimensional molecular aggregates of nanospheres and vesi-
cles tuned by solvents. The resulting controllable organic
nanoaggregate structures showed defined shapes and dimen-
sions. The optical properties of these solid nanostructures
were further studied to reveal high fluorescence in the solid
state and increased emission intensity with prolonged laser
irradiation. The mechanism is different from the fluorescent
bleaching of normal solid-state fluorescent materials; this
offers a wonderful potential application in optical devices.
Compound 6
Compound 5 (0.1 mmol) in CH2Cl2 (500 mL) was irradiated with sunlight
for about 2 h; the red solution became yellow. After the solvent was re-
moved in vacuo, the crude product was purified by column chromatogra-
phy over silica gel, eluted with CH2Cl2, to give an orange solid 6 (81 mg,
100%).[20] M.p.>3008C; 1H NMR (400 MHz, CDCl3): d=10.55 (s, 1H),
10.41 (s, 1H), 10.35 (s, 1H), 9.88 (s, 1H), 9.54 (d, J=8.6 Hz, 1H), 9.42 (d,
J=8.0 Hz, 2H), 9.21 (d, J=8.0 Hz, 2H), 8.62 (d, J=8.6 Hz, 1H), 7.63–
7.54 (m, 2H), 7.43 (dd, J=7.8, 1.4 Hz, 4H), 2.97–2.82 (m, 4H), 1.28–
1.21 ppm (m, 24H); 13C NMR (100 MHz, CDCl3): d=191.82, 164.14,
163.95, 145.87, 135.95, 134.74, 134.51, 133.18, 131.08, 130.86, 130.69,
130.01, 129.54, 129.41, 128.99, 128.30, 126.93, 126.88, 125.93, 125.81,
125.31, 124.38, 124.03, 123.95, 123.73, 123.57, 122.98, 122.89, 29.50, 24.25,
24.19 ppm; IR (KBr): n˜ =2964, 2927, 2869, 1706, 1669, 1597, 1466, 1420,
1356, 1323, 1252, 1206, 944, 815, 747, 671, 526 cmÀ1; HRMS (EI): m/z
calcd for C55H44N2O5: 812.3250; found: 812.3263.
Experimental Section
General
Compound 7
Chemicals and solvents were reagent grade; purchased from Aldrich,
ACROS Chemical Co.; and used without further purification. N,N’-
Di(2,6-diisopropylphenyl)-1-bromoperylene-3,4:9,10-tetracarboxylic acid
diimide was synthesized according to a literature procedure.[19] Silica gel
for column chromatography was purchased from JIYIDA Silica Gel
Corp. in Qing Dao (200–300 mesh). 1H and 13C NMR spectra of the
target compounds were obtained in deuterated solvents on a Bruker
ARX400 spectrometer at a constant temperature of 298 K, using tetra-
methylsilane (TMS) as the internal standard, and chemical shifts (d) are
given in ppm relative to TMS. Fast-atom bombardment and HRMS was
carried out on a VG ZabSpec mass spectrometer. Electronic absorption
spectra were measured on a JASCO V-579 spectrophotometer. Fluores-
cence excitation and emission spectra were recorded by using a Hitachi
F-4500 instrument at room temperature. Fluorescence quantum yields
were determined by the optical dilute method with PDI in CHCl3 as a ref-
erence (Ffl =1.0).
A solution of 3 (0.14 g, 0.27 mmol) and 5 (0.55 g, 0.68 mmol) in dry THF
(10 mL) was added dropwise under nitrogen to a stirred suspension of
NaH (38 mg, 1.6 mmol) in THF (5 mL) at 08C, and the mixture was
heated to 508C overnight. Water was added to quench the reaction mix-
ture, followed by extraction with dichloromethane. The combined organic
layers were dried over sodium sulfate and concentrated. Compound 7
(27 mg, 5.4% yield) was obtained after column chromatography using di-
chloromethane as the eluent. M.p.>3008C; 1H NMR (400 MHz,
CD2Cl2): d=8.78 (d, J=6.9 Hz, 8H), 8.70 (s, 2H), 8.25 (d, J=8.2 Hz,
2H), 8.16 (d, J=8.2 Hz, 2H), 7.75 (d, J=8.2 Hz, 4H), 7.62 (dd, J=16.5,
8.2 Hz, 6H), 7.51 (dt, J=11.5, 7.8 Hz, 4H), 7.36 (dd, J=11.5, 7.8 Hz,
8H), 7.29 (d, J=16.5 Hz, 2H), 7.22 (s, 2H), 4.11 (t, J=6.4 Hz, 4H), 2.76
(ddt, J=20.5, 13.6, 6.8 Hz, 8H), 1.92–1.84 (m, 4H), 1.59 (dd, J=14.9,
7.5 Hz, 4H), 1.22–1.07 (m, 48H), 1.02 ppm (t, J=7.5 Hz, 6H); 13C NMR
(100 MHz, CD2Cl2): d=164.14, 164.01, 163.88, 151.65, 146.47, 146.42,
142.23, 141.77, 138.88, 136.73, 135.82, 135.76, 135.47, 133.52, 131.96,
131.69, 131.46, 130.92, 130.75, 130.14, 129.94, 129.88, 129.48, 129.42,
128.90, 128.81, 128.34, 127.21, 124.93, 124.52, 124.46, 124.42, 123.61,
123.51, 122.73, 122.67, 110.91, 69.57, 31.96, 29.57, 29.49, 24.13, 19.89,
14.13 ppm; IR (KBr): n˜ =2961, 2927, 2867, 1705, 1666, 1591, 1463, 1405,
1340, 1249, 1199, 965, 813, 746, 667, 565 cmÀ1; MALDI-TOF: m/z: 1842.6
[C126H114N4O10]; elemental analysis calcd (%) for C126H114N4O10: C 82.06,
H 6.23, N 3.04; found: C 81.92, H 6.28, N 2.95.
General Method for Photocyclization
A dilute solution of compound in dichloromethane in a Schlenk flask
was directly placed under sunlight and a particle of iodine was added.
After the reaction was complete, the mixture was concentrated in vacuo
to afford the crude product, and further purified by column chromatogra-
phy. Cyclic voltammograms were measured at a scan rate of 100 mVsÀ1
,
using a glassy carbon electrode as the working electrode, Pt wire as the
counter electrode, SCE as the reference electrode, and nBu4NPF6 (0.1m)
in dichloromethane as the supporting electrolyte.
Compound 8
A solution of 3 (57 mg, 0.11 mmol) and 6 (227 mg, 0.28 mmol) in dry
THF (10 mL) was added dropwise under nitrogen to a stirred suspension
of NaH (16 mg, 0.66 mmol) in THF (5 mL) at 08C, and the mixture was
heated to 508C overnight. Water was added to quench the reaction mix-
ture, followed by extraction with dichloromethane. The combined organic
layer was dried over sodium sulfate and concentrated. Compound 8
(20 mg, 9.7% yield) was obtained after column chromatography using di-
chloromethane as the eluent. M.p.>3008C; 1H NMR (353 K, 300 MHz,
CDCl2CDCl2): d=10.31 (s, 2H), 10.24 (s, 2H), 9.33 (m, 8H), 9.15 (t, J=
8.6 Hz, 4H), 8.49 (d, J=8.6 Hz, 2H), 8.03 (d, J=16.4 Hz, 2H), 7.73 (d,
J=16.4 Hz, 2H), 7.58 (t, J=7.5 Hz, 4H), 7.44 (d, J=7.5 Hz, 10H), 4.29
Compound 5
A Schlenk flask was charged with N,N’-di(2,6-diisopropylphenyl)-1-bro-
moperylene-3,4:9,10-tetracarboxylic acid diimide (200 mg, 0.25 mmol),
TBAB (40 mg, 0.12 mmol), 4 (70 mg, 0.30 mmol), THF (15 mL), and
a 2m solution of sodium carbonate in water under argon. After 10 min,
[PdACHTUNGTRENNUNG(PPh3)4] (12 mg, 0.01 mmol) was added. The mixture was stirred at
758C overnight. After being cooled to room temperature, the mixture
was diluted with dichloromethane and washed with water and saturated
NaCl (aq.). Upon drying over anhydrous Na2SO4, the organic layer was
condensed in vacuo and the crude product was purified by column chro-
Chem. Asian J. 2012, 7, 2904 – 2911
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
2909

Yongjun Li, Yuliang Li, et al.
FULL PAPER
(t, J=5.0 Hz, 4H), 2.99–2.92 (m, 8H), 2.12–1.99 (m, 4H), 1.81–1.69 (m,
4H), 1.32 (m, 48H), 1.15 ppm (t, J=7.3 Hz, 6H); 13C NMR (100 MHz,
CDCl3): d=164.12, 163.91, 163.87, 163.80, 163.48, 151.60, 146.00, 145.92,
145.88, 145.86, 145.77, 145.74, 138.98, 138.95, 133.62, 133.58, 133.56,
133.50, 133.48, 133.42, 130.94, 130.87, 129.96, 129.88, 129.83, 128.04,
128.00, 127.98, 127.93, 127.87, 127.83, 127.76, 127.42, 126.56, 126.51,
124.53, 124.38, 124.21, 124.17, 124.14, 124.10, 122.94, 122.87, 122.80,
122.60, 122.57, 122.49, 122.37, 69.04, 31.82, 29.76, 29.67, 24.45, 19.75,
14.25 ppm; IR (KBr): n˜ =2961, 2926, 2864, 1708, 1668, 1598, 1465, 1423,
1357, 1326, 1251, 1198, 965, 814, 747, 667, 525 cmÀ1; MALDI-TOF: m/z:
1862.2 [C126H110N4O10 +Na+]; elemental analysis calcd (%) for
C126H110N4O10: C 82.24, H 6.02, N 3.04; found: C 82.01, H 6.17, N 3.08.
Zhuang, F. Lu, D. Zhu, J. Org. Chem. 2004, 69, 9049–9054; k) Y.
Liu, J. Zhuang, H. Liu, Y. Li, F. Lu, H. Gan, T. Jiu, N. Wang, X. He,
D. Zhu, ChemPhysChem 2004, 5, 1210–1215; l) Y. Liu, S. Xiao, H.
Li, Y. Li, H. Liu, F. Lu, J. Zhuang, D. Zhu, J. Phys. Chem. B 2004,
108, 6256–6260; m) L. Zhao, W. Yang, Y. Ma, J. Yao, Y. Li, H. Liu,
Chem. Commun. 2003, 2442–2443; n) H. Liu, Y. Li, S. Xiao, H.
Gan, T. Jiu, H. Li, L. Jiang, D. Zhu, D. Yu, B. Xiang, Y. Chen, J.
Am. Chem. Soc. 2003, 125, 10794–10795; o) Y. Li, Z. Qing, Y. Yu,
T. Liu, R. Jiang, Y. Li, Chem. Asian J. 2012, 7, 1934–1939.
[8] a) J. Cornil, D. Beljonne, J. P. Calbert, J. L. Brꢂdas, Adv. Mater.
2001, 13, 1053–1067; b) H. Sun, Z. Zhao, F. C. Spano, D. Beljonne,
J. Cornil, Z. Shuai, J. L. Brꢂdas, Adv. Mater. 2003, 15, 818–822;
c) H. Langhals, T. Potrawa, H. Nçth, G. Linti, Angew. Chem. 1989,
101, 497–499; Angew. Chem. Int. Ed. Engl. 1989, 28, 478–480; d) A.
Dreuw, J. Plçtner, L. Lorenz, J. Wachtveitl, J. E. Djanhan, J. Brꢃn-
ing, T. Metz, M. Bolte, M. U. Schmidt, Angew. Chem. 2005, 117,
7961–7964; Angew. Chem. Int. Ed. 2005, 44, 7783–7786; e) A.
Datta, F. Terenziani, A. Painelli, ChemPhysChem 2006, 7, 2168–
2174; f) J. Kim, T. M. Swager, Nature 2001, 411, 1030–1034; g) Z.
Xie, B. Yang, F. Li, G. Cheng, L. Liu, G. Yang, H. Xu, L. Ye, M.
Hanif, S. Liu, D. Ma, Y. Ma, J. Am. Chem. Soc. 2005, 127, 14152–
14153.
Acknowledgements
This study was supported by the National Basic Research 973 Program of
China (2011CB932302 and 2012CD932900) and the National Nature Sci-
ence Foundation of China (201031006).
[9] a) M. D. Curtis, J. Cao, J. W. Kampf, J. Am. Chem. Soc. 2004, 126,
4318–4328; b) G. S. Papaefstathiou, Z. Zhong, L. Geng, L. R. Mac-
Gillivray, J. Am. Chem. Soc. 2004, 126, 9158–9159; c) J.-S. Yang, J.-
L. Yan, C.-Y. Hwang, S.-Y. Chiou, K.-L. Liau, H.-H. Gavin Tsai, G.-
H. Lee, S.-M. Peng, J. Am. Chem. Soc. 2006, 128, 14109–14119;
d) A. Kishimura, T. Yamashita, K. Yamaguchi, T. Aida, Nat. Mater.
2005, 4, 546–549; e) Y. Mizobe, N. Tohnai, M. Miyata, Y. Hasegawa,
Chem. Commun. 2005, 1839–1841; f) H. Tong, Y. Dong, Hau,
J. W. Y. Lam, H. H. Y. Sung, I. D. Williams, J. Sun, B. Z. Tang,
Chem. Commun. 2006, 1133–1135; g) Y. Mizobe, H. Ito, I. Hisaki,
M. Miyata, Y. Hasegawa, N. Tohnai, Chem. Commun. 2006, 2126–
2128; h) H. Liu, J. Xu, Y. Li, Y. Li, Acc. Chem. Res. 2010, 43, 1496–
1508.
[1] a) J. M. Tour, Chem. Rev. 1996, 96, 537–554; b) U. H. F. Bunz,
Chem. Rev. 2000, 100, 1605–1644; c) M. Bendikov, F. Wudl, D. F.
Perepichka, Chem. Rev. 2004, 104, 4891–4946; d) J.-L. Brꢂdas, D.
Beljonne, V. Coropceanu, J. Cornil, Chem. Rev. 2004, 104, 4971–
5004; e) F. J. M. Hoeben, P. Jonkheijm, E. W. Meijer, A. P. H. J.
Schenning, Chem. Rev. 2005, 105, 1491–1546; f) S. R. Forrest,
Nature 2004, 428, 911–918; g) H. Meng, F. Sun, M. B. Goldfinger, F.
Gao, D. J. Londono, W. J. Marshal, G. S. Blackman, K. D. Dobbs,
D. E. Keys, J. Am. Chem. Soc. 2006, 128, 9304–9305.
[2] a) J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K.
Mackay, R. H. Friend, P. L. Burns, A. B. Holmes, Nature 1990, 347,
539–541; b) Y. Yamaguchi, T. Ochi, S. Miyamura, T. Tanaka, S. Ko-
bayashi, T. Wakamiya, Y. Matsubara, Z.-i. Yoshida, J. Am. Chem.
Soc. 2006, 128, 4504–4505; c) N. Armaroli, G. Accorsi, M. Holler,
O. Moudam, J. F. Nierengarten, Z. Zhou, R. T. Wegh, R. Welter,
Adv. Mater. 2006, 18, 1313–1316.
[10] a) A. B. Koren, M. D. Curtis, A. H. Francis, J. W. Kampf, J. Am.
Chem. Soc. 2003, 125, 5040–5050; b) B. R. Crenshaw, C. Weder,
Adv. Mater. 2005, 17, 1471–1476.
[11] F. He, H. Xu, B. Yang, Y. Duan, L. L. Tian, K. K. Huang, Y. G. Ma,
S. Y. Liu, S. H. Feng, J. C. Shen, Adv. Mater. 2005, 17, 2710–2714.
[12] a) K.-T. Wong, Y.-Y. Chien, R.-T. Chen, C.-F. Wang, Y.-T. Lin, H.-H.
Chiang, P.-Y. Hsieh, C.-C. Wu, C. H. Chou, Y. O. Su, G.-H. Lee, S.-
M. Peng, J. Am. Chem. Soc. 2002, 124, 11576–11577; b) J. N. Wilson,
M. D. Smith, V. Enkelmann, U. H. F. Bunz, Chem. Commun. 2004,
1700–1701; c) V. de Halleux, J. P. Calbert, P. Brocorens, J. Cornil,
J. P. Declercq, J. L. Brꢂdas, Y. Geerts, Adv. Funct. Mater. 2004, 14,
649–659; d) C. L. Chiang, M. F. Wu, D. C. Dai, Y. S. Wen, J. K.
Wang, C. T. Chen, Adv. Funct. Mater. 2005, 15, 231–238; e) A.
Al Ouahabi, P. N. W. Baxter, J.-P. Gisselbrecht, A. De Cian, L.
Brelot, N. Kyritsakas-Gruber, J. Org. Chem. 2009, 74, 4675–4689;
f) M. J. Frampton, H. L. Anderson, Angew. Chem. 2007, 119, 1046–
1083; Angew. Chem. Int. Ed. 2007, 46, 1028–1064.
[3] a) F. Garnier, R. Hajlaoui, A. Yassar, P. Srivastava, Science 1994,
265, 1684–1686; b) X.-C. Li, H. Sirringhaus, F. Garnier, A. B.
Holmes, S. C. Moratti, N. Feeder, W. Clegg, S. J. Teat, R. H. Friend,
J. Am. Chem. Soc. 1998, 120, 2206–2207; c) C. D. Dimitrakopoulos,
P. R. L. Malenfant, Adv. Mater. 2002, 14, 99–117.
[4] a) N. S. S. Kumar, S. Varghese, G. Narayan, S. Das, Angew. Chem.
2006, 118, 6465–6469; Angew. Chem. Int. Ed. 2006, 45, 6317–6321;
b) S. Abraham, V. A. Mallia, K. V. Ratheesh, N. Tamaoki, S. Das, J.
Am. Chem. Soc. 2006, 128, 7692–7698.
[5] a) H. V. R. Dias, H. V. K. Diyabalanage, M. G. Eldabaja, O. Elbjeir-
ami, M. A. Rawashdeh-Omary, M. A. Omary, J. Am. Chem. Soc.
2005, 127, 7489–7501; b) P. Wang, J.-P. Ma, Y.-B. Dong, Chem. Eur.
J. 2009, 15, 10432–10445; c) M. Enomoto, A. Kishimura, T. Aida, J.
Am. Chem. Soc. 2001, 123, 5608–5609.
[13] Z. Fei, N. Kocher, C. J. Mohrschladt, H. Ihmels, D. Stalke, Angew.
Chem. 2003, 115, 807–811; Angew. Chem. Int. Ed. 2003, 42, 783–
787.
[14] a) J. Eldo, E. Arunkumar, A. Ajayaghosh, Tetrahedron Lett. 2000,
41, 6241–6244; b) M. Miura, T. Koike, T. Ishihara, S. Sakamoto, M.
Okada, M. Ohta, S. i. Tsukamoto, Synth. Commun. 2007, 37, 667–
674.
[6] a) T. Mutai, H. Satou, K. Araki, Nat. Mater. 2005, 4, 685–687; b) Y.
Sagara, T. Mutai, I. Yoshikawa, K. Araki, J. Am. Chem. Soc. 2007,
129, 1520–1521; c) R. Davis, N. S. Saleesh Kumar, S. Abraham,
C. H. Suresh, N. P. Rath, N. Tamaoki, S. Das, J. Phys. Chem. C 2008,
112, 2137–2146.
[7] a) J.-M. Lehn, Science 2002, 295, 2400–2403; b) G. M. Whitesides, B.
Grzybowski, Science 2002, 295, 2418–2421; c) D. N. Reinhoudt, M.
Crego-Calama, Science 2002, 295, 2403–2407; d) T. Kato, Science
2002, 295, 2414–2418; e) T. Kato, N. Mizoshita, K. Kishimoto,
Angew. Chem. 2006, 118, 44–74; Angew. Chem. Int. Ed. 2006, 45,
38–68; f) T. Ikeda, J.-i. Mamiya, Y. Yu, Angew. Chem. 2007, 119,
512–535; Angew. Chem. Int. Ed. 2007, 46, 506–528; g) H. Zheng, Y.
Li, H. Liu, X. Yin, Y. Li, Chem. Soc. Rev. 2011, 40, 4506–4524; h) J.
Lv, Y. Zhao, G. Li, Y. Li, H. Liu, Y. Li, D. Zhu, S. Wang, Langmuir
2009, 25, 11351–11357; i) Y. Li, N. Wang, H. Gan, H. Liu, H. Li, Y.
Li, X. He, C. Huang, S. Cui, S. Wang, D. Zhu, J. Org. Chem. 2005,
70, 9686–9692; j) Y. Liu, Y. Li, L. Jiang, H. Gan, H. Liu, Y. Li, J.
[15] C.-C. Chao, M.-k. Leung, Y. O. Su, K.-Y. Chiu, T.-H. Lin, S.-J. Shieh,
S.-C. Lin, J. Org. Chem. 2005, 70, 4323–4331.
[16] a) D. M. de Leeuw, M. M. J. Simenon, A. R. Brown, R. E. F. Einer-
hand, Synth. Met. 1997, 87, 53–59; b) Y. Li, Y. Cao, J. Gao, D.
Wang, G. Yu, A. J. Heeger, Synth. Met. 1999, 99, 243–248.
[17] T. W. G. Solomons, C. B. Fryhle, Organic Chemistry, 8th ed., 2004,
p. 393.
[18] Gaussian 03, Revision C.02, M. J. Frisch, G. W. Trucks, H. B. Schle-
gel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgom-
ery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S.
2910
www.chemasianj.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2012, 7, 2904 – 2911

A Perylene Diimide Derivative
Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani,
N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K.
Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,
O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian,
J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E.
Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J.
Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C.
Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari,
J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cio-
slowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaro-
mi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng,
A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W.
Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Wall-
ingford, CT, 2004.
[19] U. Rohr, P. Schlichting, A. Bçhm, M. Gross, K. Meerholz, C.
Brꢄuchle, K. Mꢃllen, Angew. Chem. 1998, 110, 1463–1467; Angew.
Chem. Int. Ed. 1998, 37, 1434–1437.
[20] a) Y. Li, H. Zheng, Y. Li, S. Wang, Z. Wu, P. Liu, Z. Gao, H. Liu, D.
Zhu, J. Org. Chem. 2007, 72, 2878–2885; b) Y. Li, Y. Li, J. Li, C. Li,
X. Liu, M. Yuan, H. Liu, S. Wang, Chem. Eur. J. 2006, 12, 8378–
8385; c) Y. Li, L. Xu, T. Liu, Y. Yu, H. Liu, Y. Li, D. Zhu, Org. Lett.
2011, 13, 5692–5695.
Received: July 20, 2012
Published online: October 4, 2012
Chem. Asian J. 2012, 7, 2904 – 2911
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
2911