Photonic logic gates based on control of FRET by a solvatochromic perylene bisimide

Article abstract of DOI:10.1021/jo0624748

(Chemical Equation Presented) New perylenebisimide derivatives hydroxyperylenebisimide and naphthoperylenebisimide were obtained and applied to construct a new solvatochromic dyad 9. The solvatochromic behavior of hydroxyperylenebisimide was studied, and

Full text of DOI:10.1021/jo0624748

Photonic Logic Gates Based on Control of FRET by a
Solvatochromic Perylene Bisimide
Yongjun Li, Haiyan Zheng, Yuliang Li,* Shu Wang, Ziyu Wu, Peng Liu, Zengqiang Gao,
Huibiao Liu, and Daoben Zhu
CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing
100080, People’s Republic of China, Graduate School of Chinese Academy of Sciences, Chinese Academy
of Sciences, Beijing 100080, People’s Republic of China, and Synchrotron Radiation Laboratory, Institute
of High Energy Physics, Chinese Academy of Science, Beijing 100039, People’s Republic of China
ylli@iccas.ac.cn
ReceiVed December 3, 2006
New perylenebisimide derivatives hydroxyperylenebisimide and naphthoperylenebisimide were obtained
and applied to construct a new solvatochromic dyad 9. The solvatochromic behavior of hydroxyperyle-
nebisimide was studied, and the structure of naphthoperylenebisimide was determined by X-ray
crystallography. The spectral studies indicated that the hydroxyperylenebisimide and naphthoperylenebi-
simide units of dyad 9 were strongly coupled in the ground state, and as a result the fluorescence of the
naphthoperylenebisimide unit was almost quenched and that of the hydroxyperylenebisimide unit was
greatly enhanced due to the fluorescence resonance energy transfer (FRET). As we expected, this FRET
process could be tuned with the addition of protons, base, and ferric ions. This behavior of dyad 9 could
be interpreted by a two-input INH logic gate, while in the presence of Fe(III), the ion complex of 9
could execute a two-input XOR logic gate. By changing the output signal, a combinational logic circuit
with three inputs could also be interpreted.
Introduction
signals2b,5 or by altering their chemical input.6 On the basis of
input signal multiplicity, a single molecular platform integrating
multiple recognition sites for each input is expected to respond
in parallel to a variety of reagents and thereby provide a range
of Boolean functions.7
Boolean functions at the molecular scale have been demon-
strated through detectable spectroscopic changes upon an ionic,
electronic, photonic, or thermal input1 and have led to the
interpretation of complex molecular logic gates such as AND,2
XOR,3 and INHIBIT4 functions. Several logic functions can be
integrated within a single molecule by generating multiple light
The design of organic fluorescence logic gate has provided
important contributions to the development of Boolean func-
tions.8 Solvatochromic fluorophores are especially useful for
10.1021/jo0624748 CCC: $37.00 © 2007 American Chemical Society
Published on Web 03/16/2007
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J. Org. Chem. 2007, 72, 2878-2885

Photonic Logic Gates
SCHEME 1. Synthesis of 1 and 3a
1-Hydroxyperylenebisimide 1 was synthesized by heating the
solution of N,N′-di-(2,6-diisopropylphenyl)-1-bromoperylene-
3,4:9,10-tetracarboxylic acid bisimide in DMF, in the presence
of K2CO3, KI, and trace water. Compound 3 was obtained by
photocyclization of the phenyl-subtituted perylene diimide (2).11
One of the bromo moieties of 1,7-di-bromoperylenebisimide12
was substituted by N-(tert-butoxycarbonyl) tyramine to obtain
4. Subsequently compound 5 was prepared by coupling a phenyl
group to 4 through a Suzuki reaction. Compound 6 was obtained
with photocyclization reaction in high yield. After deprotection
in acidic conditions, the resulting free amino group was coupled
with succinic anhydride to give 7. Compound 8 was obtained
with the same procedure used for compound 1. Compound 8
was deprotected and coupled with 7 to give the naphthoperyle-
nebisimide-hydroxyperylenebisimide dyad 9.
a Conditions: (i) H2O, K2CO3, KI, DMF; (ii) phenylboronic acid, K2CO3,
Pd(PPh3)4, toluene, ethanol; (iii) CH2Cl2, hV.
these purposes since they usually cover a broad range of
emission wavelengths which are dependent on external stimuli.9
Our goal is to develop systems which are operated by integrating
two independent output fluorescent channels via electron transfer
and/or energy transfers modulated by the solvatochromic
properties of fluorophores.
All the compounds were fully characterized by NMR, MS,
and IR spectra. They were highly soluble in common solvents.
The molecular structure of 3 was determined by X-ray crystal-
lographic analysis, as shown in Figure 1. The most prominent
feature of the structure of 3 was the perpendicular orientation
of the 2,6-diisopropylphenyl groups with respect to the naph-
thoperylenebisimide chromophoric unit. This lead to fully
isolated chromophores. In the given crystal structure three
molecules of chloroform were intercalated to solvate the dye
or fill the empty space created by the conformationally restricted
dye molecules.13
Results and Discussion
With these thoughts in mind, we synthesized new peryle-
nebisimide dyes 1 and 3 (Scheme 1), and incorporated them
into a dyad 9 (Scheme 2) and initiated studies of the photoin-
duced electron transfer and fluorescence resonance energy
transfer (FRET) processes in this newly well-defined dyad under
the influence of external stimulations. In this paper, we will
present the photo physic properties studies of the new dyad 9.
The results showed that metal cations and H+/OH- could switch
the FRET between the two units in dyad 9 and that 9 could
also act as a fluorescent logic gate with multiply configurable
dual outputs.10
For dyes 1 the solvatochromic properties were investigated
in several solvents with different polarity and a significant
bathochromic shift of the absorption was noted in the proton
acceptor solvents (Figure 2). And we noted that the hydrogen
bond played more important role than polarity in this case. In
proton-acceptor solvents such as acetone, DMF, and pyridine,
there were significant red shifts of the longest wavelength
absorption bands. For dye 1 the absorption maximum varied
from 542 nm in CHCl3 to 777 nm in pyridine, this positive
solvatochromic shift (235 nm) was larger than that of an
aminobenzodifuranone derivative (ABF) that exhibits the largest
positive solvatochromic shift in terms of wavelength shift (206
nm).14 Similar to that aminobenzodifuranone derivative, the
hydrogen-bond formation had more important influence on the
electronic absorption spectrum, which was attributed to the
H-bond donating ability of -OH.14b The spectra shape was like
(1) For examples, see: (a) Raymo, F. M.; Giordani, S. J. Am. Chem.
Soc. 2001, 123, 4651-4652. (b) Raymo, F. M.; Alvarado, R. J.; Giordani,
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M. N.; Stefanovic, D. Nat. Biotechnol. 2003, 21, 1069-1074. (g) Okamoto,
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Soc. 1997, 119, 7891-7892. (b) de Silva, A. P.; McClenaghan, N. D.
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(7) Margulies, D.; Melman, G.; Felder, C. E.; Arad-Yellin, R.; Shanzer,
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T.; Maxwell, P. R. S.; Rice, T. E. J. Am. Chem. Soc. 1999, 121, 1393-
1394.
that of the perylene nucleus substituted with NR2 groups.15
A
similar band appeared also for intramolecular proton transfer
between the hydroxyl and amine substituents of aminoalkyl-
naphthol.16 Addition of amines such as TEA to solutions of 9
in chloroform or THF led to the appearance of a new, low-
energy absorption band, which could be considered as the
extreme condition of the solvatochromisim (Figure S2), and we
would also use this condition for further studies.
(11) Li, Y. J.; Li, Y. L.; Li, J. B.; Li, C.H.; Liu, X. F.; Yuan, M. J. Liu,
H.B.; Wang, S. Chem.-Eur. J. 2006, 12, 8378-8385. Another way to close
such a naphtho ring: Mu¨ller, S.; Mu¨llen, K. Chem. Commun. 2005, 4045-
4046.
(12) Wu¨rthner, F.; Stepanenko, V.; Chen, Z. -J.; Saha-Mo¨ller, C. R.;
Kocher, N.; Stalke, D. J. Org. Chem. 2004, 69, 7933-7939.
(13) Wu¨rthner, F.; Ahmed, S.; Thalacker, C.; Debaerdemaeker, T.
Chem.-Eur. J. 2002, 8, 4742-4750.
(9) (a) Suppan, P.; Ghoneim, N. SolVatochromism; The Royal Society
of Chemistry, London, 1997. (b) Valeur, B. Molecular Fluorescence:
Principles and Applications; Wiley-VCH: Weinheim, Germany, 2002. (c)
Lakowicz, J. R. Principles of Fluorescence Spectroscopy, 2nd ed.; Plenum
Publishing: New York, 1999; Chapter 6.
(10) Shiraishi, Y.; Tokitoh, Y.; Hirai, T. Chem. Commun. 2005, 5316-
5318.
(14) (a) Bartkowiak, W.; Lipkowski, P. J. Mol. Model. 2005, 11, 317
-322. (b) Gorman, A. A.; Hutchings, M. G.; Wood, P. D. J. Am. Chem.
Soc. 1996, 118, 8497-8498.
(15) Zhao, Y. Y.; Wasielewski, M. R. Tetrahedron Lett. 1999, 40, 7047-
7050.
(16) Tolbert, L. M.; Nesselroth, S. M. J. Phys. Chem. 1991, 95, 10331.
J. Org. Chem, Vol. 72, No. 8, 2007 2879

Li et al.
SCHEME 2. Synthesis of the Dyad 9a
a Conditions: (i) phenylboronic acid, K2CO3, Pd(PPh3)4, toluene, ethanol; (ii) CH2Cl2, hV; (iii) TFA, CHCl3, then succinic anhydride, Et3N (TEA), CH2Cl2;
(iv) H2O, K2CO3, KI, DMF; (v) TFA, CHCl3, then 7, DMAP, EDCI‚HCl, CH2Cl2.
Figure 3a showed the UV-visible spectra of 9 as compared
with the spectra of the parent 6 and 8. Compound 9 showed
superposition features of a typical naphthoperylenebisimide and
hydroxyperylenebisimide moieties. The absorption patterns
allowed the virtually selective excitation of naphthoperylenebi-
simide moiety in 9 due to the specific band of naphthoperyle-
nebisimide at 330 nm.
Figure 3 showed a strong overlap of the emission spectrum
of dye 6 with the absorption spectrum of dye 8. According to
Fo¨rster’s theory,17 long-range through-space resonance energy
transfer is expected if such an overlap of the absorption and
emission spectra (together with some other features such as high
fluorescent quantum yields17) of the involved chromophores
occurs. Both 9 and 8 exhibited an emission maximum at
579 nm with a shoulder at 620 nm, typical of the hydroxy-
perylenebisimide moiety. For compound 9 containing two
chromophores, i.e., the hydroxyperylenebisimide and the naph-
thoperylenebisimide units, an emission from the naphthoperylene-
bisimide moiety between 500 and 540 nm could be expected.
However, compound 9 displayed almost completely quenched
naphthoperylenebisimide emission in this wavelength region and
a strong and enhanced emission of hydroxyperylenebisimide
compared with 8.
On the basis of the structural properties (bulky imide
substituents) and the excellent additivity of the absorption bands
of the two chromophoric subunits (Figure 3a) we can exclude
the possibility of intramolecular aggregation due to folding of
the flexible alkyl spacer. Such aggregation would lead to strong
coupling of the two dyes and open alternative through-bond
mechanisms of energy transfer.13,17 In addition intermolecular
FRET processes between different molecules can be ruled out
at the applied concentrations of our study because no energy
transfer became apparent for equimolar mixtures of dyes 6 and
8 (Figure S1).
Figure 4 showed the absorption spectra of dyad 9 in THF
under different experimental conditions. Addition of acid alone
had no influence on the absorption of 9. In the presence of TEA,
the absorption peak assigned to hydroxyperylenebisimide moiety
decreased and a new broad peak around 700 nm appeared.
Adding Fe(III) to the solution of 9 led to an absorption
enhancement in the range of 350-450 nm and without evident
influence on the main bands. With the combination of Fe(III)
and TEA, the absorption peak of hydroxyperylenebisimide
moiety also decreased and accompanied with a new broad peak
around 650 nm, which was mainly due to the influence of the
(17) (a) Fo¨rster, T. Discuss. Faraday Soc. 1959, 27, 7-17. (b) Turro,
N. J. Modern Molecular Photochemistry; University Science Books:
Sausalito, California, 1991; p 296.
2880 J. Org. Chem., Vol. 72, No. 8, 2007

Photonic Logic Gates
FIGURE 1. (a) X-ray crystal structure of 3. (b) Projection of the X-ray crystal structure of 3 along the b axis. (c) Projection of the X-ray crystal
structure of 3 along the c axis.
FIGURE 2. Absorption (1.1 × 10-5 M) and fluorescence spectra (1.1 × 10-6 M) of 1 in different solvents.
TEA when compared with these spectra of 9 treated with Fe-
(III) and other combination conditions. That is, due to the
solvatochromisim of the hydroxyperylenebisimide, the absorp-
tion band of hydroxyperylenebisimide varied from 560 nm at
neutral or in the presence of H+ to 700 nm in the presence of
base such as TEA (Figure 4, Figure S2-3). Thus the FRET
between naphthoperylenebisimide and hydroxyperylenebisimide
can be switched in the surroundings of base and acid. Upon
excitation of the naphthoperylenebisimide moiety (330 nm) the
molecule can switch between three distinct fluorescent states
with emission of yellow, red, or off luminescence as described
below (Figure 5). In the presence of TEA, the FRET was
switched off; the red emission of the hydroxyperylenebisimide
was replaced by the moderately enhanced yellow emission of
naphthoperylenebisimide (Figure S4). Upon additon of acid, the
FRET was switched on and the red emission of hydroxyper-
ylenebisimide was regained.
Addition of iron(III) resulted in efficient fluorescent quench-
ing18 by the bound metal ion due to the electron transfer from
naphthoperylenebisimide and hydroxyperylenebisimide to
Fe(III)19 (Figure S5). The succinamide between the two
components combined with the hydroxyl group of hydroxyper-
ylene bisimide probably form a siderophore-like Fe complex,18a
because we did not observe the same fluorescent quenching
phenomena when the separate components 6 and 8 were treated
(18) (a) Weizman, H.; Ardon, O.; Mester, B.; Libman, J.; Dwir, O.;
Hadar, Y.; Chen, Y.; Shanzer, A. J. Am. Chem. Soc. 1996, 118, 12368-
12375. (b) Bodenant, B.; Fages, F.; Delville, M.-H. J. Am. Chem. Soc. 1998,
120, 7511-7519. (c) Nudelman, R.; Ardon, O.; Hadar, Y.; Chen, Y.;
Libman, J.; Shanzer, A. J. Med. Chem. 1998, 41, 1671-1678.
(19) (a) Dobrawa, R.; Wu¨rthner, F. Chem. Commun. 2002, 1878-1879.
(b) Dobrawa, R.; Lysetska, M.; Ballester, P.; Grune, M.; Wu¨rthner, F.
Macromolecules 2005, 38, 1315-1325. (c) Li, Y. J.; Wang, N.; Gan, H.
Y.; Liu, H. B.; Li, H.; Li, Y. L.; He, X. R.; Huang, C. S.; Cui, S.; Wang,
S.; Zhu, D. B. J. Org. Chem. 2005, 70, 9686-9692.
J. Org. Chem, Vol. 72, No. 8, 2007 2881

Li et al.
FIGURE 3. (a) Absorption spectra of 6 (dashed line), 8 (dotted line), and 9 (solid line) (1.2 × 10-5 M) in THF. (b) Fluorescence spectra of 6
(dashed line), 8 (dotted line), and 9 (solid line) (1.2 × 10-6 M) in THF; excitation at 330 nm.
FIGURE 4. Absorption spectra of 5 × 10-6 M 9 in THF under
different experimental conditions. Input: 20 µL THF solution of (a) 1
M Fe (ClO4)3, (b) 1 M TFA, and (c) 1 M TEA.
FIGURE 6. Schematic presentation describing the tune of FRET
process between hydroxyperylenebisimide and naphthoperylenebisimide
units of dyad 9 with the addition of TFA, TEA, and ferric ions.
When acid (TFA) was added, the pH of the system decreased,
leading to protonation of the succinamide units, followed by
the release of the bound metal ion from the succinamide to the
hydroxyperylenebisimide, as expected from siderophore-iron-
(III) complexes in lower pH.20 Since the fluorescence of the
naphthoperylenebisimide was not quenched and that of hydroxy-
perylenebisimide was quenched by Fe(III), emission was
observed predominantly at 527 nm (Figure S6). Alternatively,
addition of base (TEA) to the ferric complex resulted in a yellow
emission at 527 nm (Figure S7), which was due to the fact that
the FRET was switched off because the absorption band of
hydroxyperylenebisimide was red-shifted (as shown in Figure
4). And TEA also helped the ionization of the hydroxyperyle-
nebisimide, so Fe(III) was easier to complex with the hydroxy-
FIGURE 5. Fluorescence spectra of 5 × 10-6 M 9 in THF excited at
perylenebisimide part. However, when both acid and base were
330 nm under different experimental conditions. Input: 20 µL THF
added, a buffer solution was formed, most of the iron remained
bound to the receptor, and the output signal remained essentially
quenched. All these situations were summarized in the Fig-
ure 6.
solution of (a) 1M Fe (ClO4)3, (b) 1 M TFA, and (c) 1 M TEA.
with Fe(III). And when we treated the more concentrated 9 in
THF with iron (III), there was some precipitates formed and
the absorption intensity of the solution decreased. And when
EDTA was added into the solution containing the precipitate,
the precipitate disappeared and the absorption intensity of the
solution was regained. With the addition of TEA or TFA, the
yellow emission of naphthoperylenebisimide was regained.
From a logic viewpoint,17,18 it could be argued that the system
such as compound 9 transduced two chemical inputs (TFA and
TEA) into one optical output (fluorescence emission at 527 nm)
(20) Monzyk, B.; Crumbliss, A. L. J. Am. Chem. Soc. 1982, 104, 4921-
4929.
2882 J. Org. Chem., Vol. 72, No. 8, 2007

Photonic Logic Gates
TABLE 1. INH Logic Gate
were strongly coupled in the ground state, and as a result the
fluorescence of the naphthoperylenebisimide unit was almost
quenched and that of the hydroxyperylenebisimide unit was
greatly enhanced due to the FRET. However, this FRET process
could be tuned with the addition of protons, base, and ferric
ions. This behavior of dyad 9 could be interpreted by a two-
input INH logic gate, while in the present of Fe(III), the ion
complex of 9 could execute a two-input XOR logic gate. By
changing the output signal, a combinational logic circuit with
three inputs could also be interpreted. The results may provide
a novel strategy for designing the complex photoelectronic
devices, in which the system was operated by integrating two
independent output fluorescent channels via electron transfer
and/or energy transfers modulated by the solvatochromic
properties of fluorophores.
input 1 (TEA)
input 2 (TFA)
outputa (λem ) 527 nm)
0
0
1
1
0
1
0
1
0
0
1
0
a At 527 nm, the fluorescence intensity bigger than double of that of the
initial solution is defined as 1, otherwise defined as 0.
TABLE 2. XOR Logic Gate
input 1 (TEA)
input 2 (TFA)
output (λem ) 527 nm)
0
0
1
1
0
1
0
1
0
1
1
0
TABLE 3. Truth Table for All Possible Strings of Three
Binary-Input Data and the Corresponding Output Digit
(Combinational Logic Circuit Corresponding to This Truth Table Is
Given in Figure 7)
Experimental Section
Crystallography. Single crystals of 3, C57H47N2O4Cl9 (M )
1143.02), were obtained by slow diffusion of methanol into a
solution of 3 in CHCl3. The unit cell was monoclinic, space group
P21/n, a ) 11.064 (2), b ) 38.215 (8), c ) 12.976 (3) Å, R )
90.00, â ) 104.53(3), γ ) 90.00°, V ) 5310.8(18)Å3, Z ) 4, Fcalcd
input
outputa
I1 (Fe3+
)
I2 (TEA)
I3 (TFA)
O (λem ) 580 nm)
2
2
) 1.430 g cm-3; R ) 0.1011(4255 data with F0 > 2θ(F0 )), and
678 refined parameters. A total of 4255 native data was collected
at T ) 200 K on a MARCCD detector at a synchrotron radiation
beam line 3W1A, and the wavelength is 0.9 Å. A crystal-to-detector
distance (70 mm) and an oscillation (5.0°) are necessary for getting
diffraction data with higher quality. Data were processed with
HKL2000. All data have been collected with the storage ring
working at the energy of 2.2 GeV and with a current decreasing
by about 135 mA to 80 mA during a time span of 8 h. The structure
was solved by direct methods and refined by full-matrix least-
squares on F2 values of all data (SHELXTL), all non-hydrogen
atoms were refined isotropically, whereby all hydrogen atoms were
placed at their idealized positions.
0
0
0
0
1
1
1
0
0
1
1
0
0
1
0
1
0
1
0
1
0
1
1
0
1
0
0
0
a At 580 nm, the fluorescence intensity bigger than half of that of the
initial solution is defined as 1, otherwise defined as 0.
General Method for Suzuki Coupling. N,N′-Di-(2,6-diisopro-
pylphenyl)-1-bromoperylene-3,4:9,10-tetracarboxylic acid bisimide
or N,N′-di-(2,6-diisopropylphenyl)-1,7-dibromoperylene-3,4:9,10-
tetracarboxylic acid bisimide and boronic acid were dissolved in
toluene/ethanol (30 mL/10 mL), and 50 mg of K2CO3 was added.
The solution was degassed by bubbling N2 for 30 min. Then Pd
(PPh3)4 (about 5 mg) was added. The reaction mixture was allowed
to stir at 80 °C for 3 h and then reduced in volume and the resulting
solid taken up with CH2Cl2 (50 mL) and washed with H2O (1 ×
20 mL). The organic layer was dried over anhydrous Na2SO4 and
filtered, and the solvent removed under reduced pressure to obtain
a black solid, which was purified by column chromatography (CH2-
Cl2 as eluent).
General Method for Photocyclization. Compounds for cycliza-
tion (0.02-0.03 mmol) were dissolved in CH2Cl2 (20 mL) in a
quartz vessel. The solution was directly irradiated in the sun. The
progress was monitored by thin-layer chromatography (TLC). After
the photocyclization was finished, the reaction mixture was
concentrated under reduced pressure to afford the crude product
and purified by column chromatography (CH2Cl2 as eluent).
1. 1 was synthesized by heating the solution of N,N′-di-(2,6-
diisopropylphenyl)-1-bromoperylene-3,4:9,10-tetracarboxylic acid
bisimide (32 mg, 0.04 mmol) in DMF (10 mL) at 100 °C for 10 h,
in the presence of K2CO3 (10 equiv), KI (2 equiv), and trace water.
The reaction mixture was concentrated under reduced pressure to
afford the crude product and purified by column chromatography
on silica with CH2Cl2/MeOH (20/1) to afford 1 (22 mg, yield 76%).
1H NMR (400 MHz, CDCl3), δ 9.86 (d, 1 H, J) 8.4 Hz), 8.82-
8.78 (m, 3 H), 8.75 (d, 1 H, J ) 8.1 Hz), 8.66 (d, 1 H J ) 8.0 Hz),
8.35 (s, 1 H), 7.55-7.48 (m, 2 H), 7.38-7.35 (m, 4 H), 3.41 (s, 1
H), 2.78-2.72 (m, 4 H), 1.21-1.17 (m, 24 H). HRMS calcd
727.3166 (C48H43N2O5, M + H), observed 727.3157.
FIGURE 7. The combinational logic circuit equivalent to the truth
table given in Table 3.
through an inhibit (INH) operation. In either acid or buffered
solution condition, the FRET between naphthoperylenebisimide
and hydroxyperylenebisimide was on and the emission at 527
nm was weak. The emission at 527 nm was relatively high only
when base was added and no acid was added. If a positive logic
convention (low ) 0, high ) 1) was applied to all signals, the
signal transduction behavior of 9 translated into the truth table
of a two-input INH circuit (Table 1). The output O is equal to
1 only when I1 is 1 and I2 is 0. In the presence of Fe(III), the
ion complex of 9 responded to two inputs (TFA and TEA)
producing one optical output (fluorescence emission at 527 nm)
through a XOR operation (Table 2). When the output was
defined as fluorescence emissions at 580 nm, a more compli-
cated combinational logic circuit with three inputs (Fe3+, TEA,
and TFA) can be executed through a series of AND, NOT, and
OR operations. The corresponding truth table was presented in
Table 3, and the combinational logic circuit was shown in Figure
7.
Conclusion
In summary, the spectral studies indicated that the hydroxy-
perylenebisimide and naphthoperylenebisimide units of dyad 9
J. Org. Chem, Vol. 72, No. 8, 2007 2883

Li et al.
2. N,N′-Di-(2,6-diisopropylphenyl)-1-bromoperylene-3,4:9,10-
tetracarboxylic acid bisimide (316 mg, 0.4 mmol) and phenylboronic
acid (74 mg, 0.6 mmol) reacted according to the general method
7.58-7.53 (m, 2 H), 7.43-7.39 (m, 2 H), 7.32 (d, 2 H, J ) 8.3
Hz), 7.24 (d, 2 H, J ) 8.3 Hz), 4.70 (s, 1 H), 3.43 (m, 2 H), 2.92-
2.85 (m, 6 H), 1.46 (s, 9 H), 1.29-1.19 (m, 24 H). 13C NMR (100
MHz, CDCl3), δ 171.1,164.0, 163.8, 163.7, 163.4, 156.5, 156.0,
153.6, 145.8, 136.5, 133.2, 131.1, 130.8, 130.6, 130.5, 129.8, 129.2,
129.0, 128.8, 128.4, 128.0, 127.8, 127.3, 127.2, 127.1, 126.6, 125.2,
124.7, 124.6, 124.2, 124.0, 123.7, 123.3, 122.4, 122.3, 122.1, 121.7,
119.9, 66.4, 41.9, 35.7, 29.5, 29.4, 28.5, 24.3, 24.2, 24.2, 24.1. IR
(KBr) ν 3368, 3067, 2965, 2929, 2870, 1710, 1670, 1620, 1597,
1525, 1502, 1469, 1435, 1379, 1328, 1282, 1258, 1204, 1167, 745
cm-1. MS TOF calcd 1019.45 (C67H61N3O7), observed 1019.7. Anal.
calcd for C67H61N3O7: C, 78.88; H, 6.03; N, 4.12. Found: C, 78.91;
H, 6.06; N, 4.08.
1
to give 2 (258 mg, yield 82%). H NMR (400 MHz, CDCl3), δ
∼8.80-8.68 (m, 5 H), 8.23 (d, 1 H, J ) 9 Hz), 7.96 (d, 1 H, J )
9 Hz), ∼7.58-7.44 (m, 7 H), ∼7.35-7.26 (m, 2 H), ∼2.78-2.73
(m, 4 H), ∼1.26-1.14 (m, 24 H). MS TOF calcd 786.35-
(C54H46N2O4), observed 786.5. Anal. calcd (%) for C54H46N2O4:
C, 82.42; H, 5.89; N, 3.56. Found: C, 84.47; H, 5.81; N, 3.63.
3. According to general method for photocyclization, 100 mg
of 2 in 100 mL CH2Cl2 was directly irradiated in the sun for 3 h.
The reaction mixture was concentrated under reduced pressure to
afford the crude product and purified by column chromatography
1
on silica with CH2Cl2 to afford 3 (92 mg, yield 92%). H NMR
7. To a stirred solution of 6 (152 mg, 0.15 mmol) in anhydrous
CHCl3 (10 mL) was added TFA (2 mL). The solution was stirred
until the deprotection was complete by TLC; then the solution was
reduced in volume and the excess of TFA removed in vacuo. The
resulting solid was taken up in anhydrous CH2Cl2 (50 mL), and
one drop of Et3N was added. Then a solution of succinic anhydride
(50 mg, 0.5 mmol) in CH2Cl2 (5 mL) was added slowly over 30
min. After 16 h, the solution was reduced in volume and purification
was accomplished by column chromatography on silica with CH2-
(300 MHz, CDCl3), δ 10.34 (s, 2 H), 9.42-9.39 (m, 2 H), 9.37 (d,
2 H, J ) 8.3 Hz), 9.16 (d, 2 H, J ) 8.1 Hz), 8.18-8.15 (m, 2 H),
7.56 (t, 2 H, J ) 7.6 Hz), 7.42 (d, 4 H, J ) 7.7 Hz), 2.92-2.85
(m, 4 H), 1.26-1.22 (m, 24 H). IR: 2959, 2926, 1699, 1661, 1591,
1429, 1353, 1324, 1254, 910, 837, 728. MS TOF calcd 784.33
(C54H44N2O4), observed 784.6. Anal. calcd for C54H44N2O4: C,
82.63; H, 5.65; N, 3.57. Found: C, 82.76; H, 5.59; N, 3.49.
4. A mixture of tert-butyl-4-hydroxyphenethylcarbamate (166 mg,
0.7 mmol), anhydrous potassium carbonate (97 mg, 0.7 mmol), and
18-crown-6 (184 mg, 0.7 mmol) was stirred in toluene (50 mL) at
room temperature. Then N,N′-di-(2,6-diisopropylphenyl)-1-bro-
moperylene-3,4:9,10-tetracarboxylic acid bisimide (866 mg, 1.0
mmol) was added. The reaction mixture was refluxed under nitrogen
with stirring for 2 h. After cooling to room temperature, the solvent
was removed by reduced pressure, and the crude product was
obtained. Purification was accomplished by column chromatography
on silica with CH2Cl2 to give 4 (510 mg, 71%): 1H NMR (400
MHz, CDCl3), δ 9.69-9.63 (m, 1 H), 9.49-9.44 (m, 1 H), 9.04-
8.98 (m, 1 H), 8.83-8.74 (m, 2 H), 8.39-8.37 (m, 1 H), 7.52-
7.46 (m, 2 H), 7.36-7.32 (m, 4 H), 7.27 (d, 2 H, J ) 8.4 Hz), 7.11
(d, 2 H, J ) 8.4 Hz), 4.59 (s, 1 H), 3.41-3.36 (m, 2 H), 2.83 (t,
2 H, J ) 6.8 Hz), 2.78-2.67 (m, 4 H), 1.43 (s, 9 H), 1.19-1.14
(m, 24 H). 13C NMR (100 MHz, CDCl3), δ 163.5, 163.3, 163.2,
162.8, 162.6, 162.5, 155.9, 155.6, 153.5, 145.6, 138.5, 137.5, 136.2,
134.3, 133.6, 133.1, 131.9, 131.0, 130.9, 130.3, 130.3, 129.8, 129.8,
129.7, 129.7, 129.7, 129.3, 129.0, 128.8, 128.4, 128.0, 125.5, 124.6,
124.4, 124.2, 124.1, 124.0, 123.5, 123.3, 122.6, 122.5, 122.4, 122.3,
121.7, 120.4, 119.5, 119.5, 119.4, 41.8, 35.6, 29.2, 29.2, 28.4, 24.0,
23.8. IR (KBr) ν 3396, 3066, 2964, 2929, 2870, 1709, 1670, 1592,
1502, 1469, 1398, 1337, 1261, 1201, 1168, 737 cm-1. MS TOF
calcd 1023.35 (C61H58BrN3O7), observed 1023.2. Anal. calcd for
C61H58BrN3O7: C, 71.48; H, 5.70; N, 4.10. Found: C, 71.51; H,
5.57; N, 4.08.
1
Cl2/MeOH (10/1) to give 7 (99 mg, yield 65%). H NMR (400
MHz, CDCl3), δ 10.29 (s, 1 H), 10.27-10.25 (m, 1 H), 10.23
(s, 1 H), 9.38-9.32 (m, 2 H), 9.11 (d, 1 H, J ) 4.6 Hz), 8.72
(s, 1 H), 8.20-8.13 (m, 2 H), 7.57-7.51 (m, 2 H), 7.42-7.37
(m, 4 H), 7.34 (d, 2 H, J ) 8.4 Hz), 7.28 (d, 2 H, J ) 8.4 Hz),
6.21 (s, 1 H), 3.60 (t, 2 H, J ) 6.0 Hz), 2.92-2.86 (m, 4 H), 2.83
(t, 2 H, J ) 6.8 Hz), 2.63 (t, 2 H, J ) 6.4 Hz), 2.48 (t, 2 H, J )
6.4 Hz), 1.27-1.15 (m, 24 H). MS TOF calcd 1020.17 (C66H57N3O8),
observed 1020.3. Anal. calcd for C66H57N3O8: C, 77.70; H, 5.63;
N, 4.12. Found: C, 77.68; H, 5.59; N, 4.14.
8. The solution of 4 (102 mg, 0.1mmol) in DMF (10 mL) was
heated at 100 °C for 10 h, in the presence of K2CO3 (10 equiv), KI
(2 equiv), and trace water. The reaction mixture was concentrated
under reduced pressure to afford the crude product and purified by
column chromatography on silica with CH2Cl2/MeOH (20/1) to
afford 8 (75 mg, yield 78%). 1H NMR (400 MHz, CDCl3), δ 9.68
(d, 1 H, J ) 8.6 Hz), 9.63 (d, 1 H, J ) 8.2 Hz), 8.88 (s, 1 H), 8.77
(d, 1 H, J ) 8.1 Hz), 8.62 (d, 1 H, J ) 8.6 Hz), 8.42 (s, 1 H),
7.60-7.56 (m, 1 H), 7.52-7.46 (m, 1 H), 7.40 (d, 2 H, J ) 7.8
Hz), 7.33 (d, 2 H, J ) 7.5 Hz), 7.23 (d, 2 H, J ) 7.3 Hz), 7.08
(d, 2 H, J ) 7.3 Hz), 4.61 (s, 1 H), 3.40-3.36 (m, 2 H), 2.81-
2.71 (m, 6 H), 1.43 (s, 9 H), 1.18-1.14 (m, 24 H). 13C NMR (100
MHz, CDCl3), δ 164.3, 163.8, 163.6, 163.3, 156.3, 156.2, 154.4,
153.9, 145.7, 145.7, 135.5, 135.3, 133.4, 130.9, 130.8, 130.5, 130.3,
129.8, 129.6, 129.5, 129.3, 128.8, 128.6, 126.1, 125.5, 125.2, 124.3,
124.1, 123.5, 123.1, 122.0, 121.0, 119.3, 119.0, 41.8, 35.5, 29.7,
29.2, 28.4, 24.0. MS TOF calcd 962.14 (C61H59N3O8), observed
962.1. Anal. calcd for C61H59N3O8: C, 76.15; H, 6.18; N, 4.37.
Found: C, 76.22; H, 6.14; N, 4.39.
9. To a stirred solution of 8 (50 mg, 0.05 mmol) in anhydrous
CHCl3 (10 mL) was added TFA (2 mL). The solution was stirred
until the deprotection was complete by TLC; then the solution was
reduced in volume and the excess of TFA removed in vacuo. The
resulting solid was purified by column chromatography roughly
(CHCl3/MeOH, 10/1). The resulting solid was taken up in anydrous
CH2Cl2 (50 mL), and 4-DMAP (12.5 mg, 0.1 mmol), 7 (61 mg,
0.06 mmol), and EDCI‚HCl (19.5 mg, 0.1 mmol) were added
sequentially under cooling with an ice bath. And the solution was
allowed to stir for 16 h. The reaction mixture was washed with a
saturated solution of citric acid (3 × 20 mL) and H2O (3 × 20
mL). The organic layer was dried over anhydrous MgSO4 and
filtrated, and the filtrate reduced in volume and the resulting solid
purified by chromatography on silica gel using a gradient of CH2-
Cl2 to CH2Cl2/MeOH (20/1) to obtain the desired compound as a
red powder (9, 42 mg, 45%, there are some product that coupled
with the hydroxyl group of compound 8, which was separated
during the chromatography). 1H NMR (400 MHz, CDCl3), δ 10.30
5. 4 (205 mg, 0.2mmol) and phenylboronic acid (69 mg,
0.5mmol) reacted according to the general Suzuki coupling method
1
to give 5 (200 mg, 98%). H NMR (400 MHz, CDCl3), δ 9.54-
9.49 (m, 1 H), 8.75-8.67 (m, 2 H), 8.38 (s, 1 H), 8.22-8.16 (m,
1 H), 8.04-7.96 (m, 1 H), 7.60-7.46 (m, 7 H), 7.35-7.29 (m, 4
H), 7.27 (d, 2 H, J ) 8.4 Hz), 7.14 (d, 2 H, J ) 8.4 Hz), 4.67-
4.51 (br, 1 H), 3.39 (m, 2 H), 2.83 (m, 2 H), 2.77-2.70 (m, 4 H),
1.43 (s, 9 H), 1.18-1.14 (m, 24 H). 13C NMR (100 MHz, CDCl3),
δ 163.5, 163.5, 163.3,162.8,155.8, 155.3, 153.7,145.6, 145.6, 145.6,
145.5, 142.4, 141.2, 125.9, 135.8,134.8, 134.8, 133.9,133.0, 131.9,
131.7, 130.9, 130.8, 130.5, 130.3, 130.1, 129.9, 129.8, 129.6, 129.1,
128.8, 128.6, 128.5, 125.8, 124.9, 124.4, 124.2, 124.0, 123.9, 122.3,
122.1, 121.9,119.3, 119.2, 41.7, 35.6, 29.2, 29.1, 28.3, 24.1, 23.9.
IR (KBr) ν 3395, 3062, 2964, 2929, 2870, 1707, 1669, 1593, 1502,
1469, 1405, 1333, 1262, 1201, 1168, 737 cm-1. MS TOF calcd
1021.47 (C67H63N3O7), observed 1021.6. Anal. calcd for
C67H63N3O7: C, 78.72; H, 6.21; N, 4.11. Found: C, 78.77; H, 6.17;
N, 4.13.
6. 6 was gained according to general method for photocyclization
(yield 90%). 1H NMR (400 MHz, CDCl3), δ 10.37 (s, 1 H), 10.32
(s, 1 H), 10.31 (d, 1 H, J ) 8.5 Hz), 9.41 (d, 2 H, J ) 5.4 Hz),
9.12 (d, 1 H, J ) 8.5 Hz), 8.74 (s, 1 H), 8.19-8.16 (m, 2 H),
2884 J. Org. Chem., Vol. 72, No. 8, 2007

Photonic Logic Gates
(s, 1 H), 10.22 (d, 1 H, J ) 8.5 Hz), 10.16 (s, 1 H), 9.66 (d, 1 H,
J ) 8.3 Hz), 9.45 (d, 1 H, J ) 8.1 Hz), 9.40-9.34 (m, 1 H), 9.34-
9.26 (m, 1 H), 9.06 (d, 1 H, J ) 8.6 Hz), 8.78 (s, 1 H), 8.67 (s, 1
H), 8.62 (d, 1 H, J ) 8.0 Hz), 8.47 (d, 1 H, J ) 8.1 Hz), 8.30 (s,
1 H), 8.13-8.06 (m, 2 H), 7.57-7.51 (m, 2 H), 7.42-7.34 (m, 6
H), 7.33-7.28 (m, 4 H), 7.24-7.17 (m, 8 H), 7.00 (d, 2 H, J )
7.8 Hz), 6.87 (br, 2 H), 3.50-3.41 (m, 4 H), 2.91-2.83 (m, 4 H),
2.75-2.60 (m, 8 H), 2.58-2.45 (m, 4 H), 1.26-1.05 (m, 48 H).
MS TOF calcd 1862.7 (C122H106N6O13), observed 1885.6 (M + Na),
1901.7 (M + K). Anal. calcd for C122H106N6O13: C, 78.60; H, 5.73;
N, 4.51. Found: C, 78.63; H, 5.75; N, 4.53.
Acknowledgment. This work is supported by the National
Natural Science Foundationof China (20131040, 50372070,
20418001, 20473102, and 20421101) and the National Basic
Research 973 Program of China (Grant Nos. 2005CB623602
and 2006CB806200). This project is partly supported by
National Center for Nanoscience and Technology, China.
Supporting Information Available: NMR spectral data, UV-
vis and fluoresce titration spectra of the dyad 9. This material is
available free of charge via the Internet at http://pubs.acs.org.
JO0624748
J. Org. Chem, Vol. 72, No. 8, 2007 2885