Synthesis and characterization of 3,5-bis(2-hydroxyphenyl)-1,2,4-triazole functionalized tetraaryloxy perylene bisimide and metal-directed self-assembly

Article abstract of DOI:10.1021/jo051022c

New perylene bisimide dyes bearing 3,5-bis(2-hydroxyphenyl)-1,2,4-triazole receptor units with different spacers have been synthesized and characterized. The fluorescence and electronic properties of these compounds have been studied. MALDI-TOF, UV-vis, a

Full text of DOI:10.1021/jo051022c

Synthesis and Characterization of
3,5-Bis(2-hydroxyphenyl)-1,2,4-triazole Functionalized
Tetraaryloxy Perylene Bisimide and Metal-Directed Self-Assembly
Yongjun Li,†,‡ Ning Wang,†,‡ Haiyang Gan,†,‡ Huibiao Liu,† Hao Li, Yuliang Li,*,†
Xiaorong He,†,‡ Changshui Huang,†,‡ Shuang Cui,†,‡ Shu Wang,† and Daoben Zhu*,†
CAS Key Laboratory of Organic Solids, Institute of Chemistry, and Graduate School of Chinese Academy
of Sciences, Chinese Academy of Sciences, Beijing 100080, P. R. China
ylli@iccas.ac.cn
Received May 22, 2005
New perylene bisimide dyes bearing 3,5-bis(2-hydroxyphenyl)-1,2,4-triazole receptor units with
different spacers have been synthesized and characterized. The fluorescence and electronic properties
of these compounds have been studied. MALDI-TOF, UV-vis, and fluorescence titration experiments
proved that monotopic perylene bisimide ligands could be assembled into dimmers by FeIII
coordination. The coordination properties of the ditopic perylene bisimide ligands have also been
studied preliminarily. Furthermore, the SEM images indicated that well-defined nanoscale
structures could be fabricated by self-assembly due to metal ion coordination and π-π stacking
interactions of perylene rings with the help of a proper spacer.
Introduction
constructing two- or three-dimensional supramolecular
architectures, such as macrocycles, molecular containers,
tubular structures, interlocked and intertwined struc-
tures, and helicates, which are useful in molecular or
chiral recognition, host-guest chemistry, catalysis, and
memory storage.7,8
A number of coordination polymers have been synthe-
sized mostly based on kinetically inert complexes.9
Introduction of metal ions into conjugated polymers has
Supramolecular polymers, chains of molecules con-
nected by noncovalent bonds, have attracted considerable
interest in recent years.1-6 They have many properties
in common with ordinary, covalent polymers but also
introduce new features. Metal-mediated self-assembly
has been proved to be a very effective methodology in
† CAS Key Laboratory of Organic Solids.
‡ Graduate School of Chinese Academy of Sciences.
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10.1021/jo051022c CCC: $30.25 © 2005 American Chemical Society
Published on Web 11/01/2005
9686
J. Org. Chem. 2005, 70, 9686-9692

Synthesis of Functionalized Perylene Bisimides
been investigated with regard to higher electrolumines-
cence quantum yields by harvesting triplet state emis-
sion.10 Thus metal-directed supramolecular polymeriza-
tion of photoactive building blocks might be of interest.11
Red chromophores based on perylenetetracarboxylic di-
imide recently triggered considerable attention of inves-
tigators and show possible various applications such as
fluorescent solar collectors,12 photovoltaic devices,13 dye
lasers,14 molecular switches,15 and light emitting diodes16
due to their exclusive chemical, thermal, and photochemi-
cal stability and their ability to self-assemble into
extended structures.17 They are highly absorbing in the
visible to near-IR region (ꢀ ≈ 105 M-1 cm-1) and emit
fluorescene with quantum yields near unity.18 Perylene-
based chromophoric arrays19 are promising components
for the construction of optical and electronic molecular
devices, for instance as n-type semiconductor material
in organic photovoltaic cells.20 They have been incorpo-
rated in classical polyimide main chain polymers by the
Mu¨llen and Thelakkat groups.18a,21 The Wu¨rthner group
has studied metal-directed self-assembly of highly fluo-
rescent perylene bisimides equipped with the 2,2′:6′,2′′-
terpyridine complexing unit11,22 to photoactive coordina-
tion polymers.
nitrogen atoms of the heterocycle.24 Formation of the 2:1
HL (-2H)-Fe3+ complex has a log K value of 38.6 in H2O/
DMSO (4:1), and this complex adopts a trans-N2O4
coordination.24 H3L has also a strong affinity for Al3+ (log
K ) 34.0), Cu2+ (log K ) 23.9), and Zn2+ (log K ) 17.5)
ions.
Here we report the metal-directed self-assembly of
perylenetetracarboxylic diimide connected to ligand H3L
through different spacers, which provided the opportunity
to elucidate the impact of the metal ion and spacers on
the photophysical properties of perylenetetracarboxylic
diimide and on the nanostructure of these self-assembling
photofunctional materials. For reasons of comparison and
simplicity, we also prepared monotopic perylene.
Results and Discussion
Synthesis and Characterization of Perylene Bis-
imide Ligands. A mixture of 2 and 5 was obtained by
partial saponification of the corresponding N,N′-dioctyl
perylene bisimide (1).25 Monoanhydride 2 or bisanhydride
5 was condensed with corresponding diamine in toluene
with the catalysis of imidazole26 to afford 3 or 6. The dyes
6 with two amino anchor groups were linked to the
appropriate carboxylic acid chloride of ligand H3L so that
the ditopic perylene bisimides 7 were obtained (Scheme
1). The same reaction starting with the dyes 3 afforded
the monotopic perylene bisimide ligands 4. For 4a, 4b,
7a, and 7b, the spacer units R had flexable -CH2-
linkages, while for 4c and 7c, the rigid backbone was
derived from phenylene group. The new compounds were
fully characterized by 1H NMR and 13C NMR and
MALDI-TOF mass spectroscopy.
The tridentate ligand 4-[3,5-bis(2-hydroxyphenyl)-1,2,4-
triazol-1-yl] benzoic acid (H3L),23 as a potential ligand for
Ligands 4 and 7 are dark purplish-black solids that,
once dissolved homogeneously, display the typical bright
red color that is representative for tetraphenoxy-substi-
tuted perylene bisimides. The optical absorption and
fluorescence properties of the ligands 4 and 7 and their
relative fluorescence quantum yields φF were investi-
gated.
the construction of larger polymeric aggregates, has been
shown in the literature to bind metal ions using the two
deprotonated phenolic hydroxyl groups and one of the
The UV-vis absorption spectra of 4 and 7 showed
almost unchanged absorption properties of the perylene
bisimide upon linkage with the ligand at wavelengths λ
> 350 nm (representative spectra are shown in Figure
1, and the absorption data are summarized in Table 1).
The absorption bands of the perylene unit gave the
characteristic π-π transitions of the functionalized
perylene bisimide:27,28 455 nm (S0-S2 electronic transi-
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J. Org. Chem, Vol. 70, No. 24, 2005 9687

Li et al.
SCHEME 1. Synthesis Route of the Functioned Perylene Bisimide Dyesa
a (i) KOH, isopropyl alcohol, H2O, reflux, 10 h; (ii) diamine, toluene, imidazole, reflux, 0.5 h; (iii) H3L, SOCl2, THF; (iv) Et3N, THF,
CHCl3.
FIGURE 1. UV-vis absorption and fluorescence spectra of
diamino-perylene 6a and ditopic perylene bisimide ligand 7a
(10-5 M) in CHCl3.
FIGURE 2. Normalized fluorescence spectra of 7a, 7b, and
7c in solid film (λexc ) 550 nm).
bisimide 4 and 7 in chloroform are mirror images of the
S0-S1 absorption band, and their position and vibronic
fine structure corresponded well to those unlinked with
triazol-ligand. The fluorescence quantum yields (φF)
ranged from 0.75 for 7b to 0.91 for 4a in CHCl3.
Particularly, the fluorescence spectra of 7a, 7b, and 7c
as thin film show red emission at 642, 646, and 649 nm,
respectively (Figure 2). The spacer between the H3L
ligands and the perylene bisimide affected the
fluorescence of the core perylene bisimide. These
sorts of compounds can be used as good red emission
materials.
TABLE 1. Photophysics of Perylene Bisimide Ligand
UV λmax (nm)
a
(ꢀ dm3 mol-1 cm-1
)
FL λmax (nm)
φF
4a
4b
4c
7a
7b
7c
585 (46650)
593 (44320)
589 (41160)
585 (46650)
589 (47900)
587 (51060)
623
617
614
614
620
615
0.91
0.81
0.88
0.88
0.75
0.90
a N,N′-Di(2,6-diisopropylphenyl)-1,6,7,12-tetraphenoxyperylene-
3,4,9,10-tetracarboxylic diimide (TPPI) as reference (φfl ) 0.96 in
CHCl3).14b
Synthesis and Characterization of Perylene Bis-
imide Ligand-Metal Complexes. The complexation
of the monotopic dye 4 with FeIII yields a dimeric complex,
which could be seen as a model reaction for the formation
of the coordination polymer. Complexation with FeIII
could be achieved in a mixture of chloroform and metha-
nol and can be easily demonstrated by means of MALDI-
TOF mass spectrometry, UV-vis spectroscopy, and fluo-
rescence titration experiments. Addition of Fe3+ to the
solution of 4a led to a modification of the absorption
tion), 545 and 585 nm (S0-S1 electronic transition).14b,29
At shorter wavelengths, a small increase in the absorp-
tion attributed to triazol ligand can be observed. The
fluorescence peaks obtained for the fluorescent perylene
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C. Macromolecules 2003, 36, 5918.
9688 J. Org. Chem., Vol. 70, No. 24, 2005

Synthesis of Functionalized Perylene Bisimides
FIGURE 3. UV-vis absorption titration experiment of 4a
(10-5 M) in CHCl3 with Fe (NO3)3; inset shows absorbance
change (at 350 nm) as a function of the Fe3+/ligand ratio.
FIGURE 5. Fluorescence titration experiment of 4b (10-5 M)
in CHCl3/CH3OH (100:1) with Fe (NO3)3, λexc)550 nm. Inset:
relative fluorescence intensities upon addition of Fe(NO3)3
calculated from the integrated fluorescence spectra.
FIGURE 4. MALDI-TOF spectrogram of the 4b-Fe-4b coor-
dination dimmer.
FIGURE 6. Cyclic voltammograms of 4b, 7b, and 7b + Fe3+
in 0.05 M TBAPF6, CHCl3. Scan rate ) 50 mV/s.
spectra with an increase of the absorbance at 350 nm,
almost unchanged absorption properties at wavelengths
λ > 400 nm (as shown in Figure 3), and a change of the
color of the solution from red to violet. The MALDI-TOF
mass spectrogram of 4b-FeIII complex showed a clear
dimeric complex (Figure 4), which indicated that with
vis and fluorescence spectra, there were evident elec-
tronic interactions between the FeL2 unit and the perylene
bisimide chromophore: FeIII as a good electron acceptor
quenched the excited state of the perylene bisimide
through electron transfer.
FeIII this ligand preferred to form bis complex [FeL2]3-
,
whereas in the case of ditopic perylene bisimide 7, only
fragments showing the ligand with one Fe3+ could be
observed. (The mass fractions of higher-molecular-weight
oligomers or polymers were absent due to the opening of
the iron(III)-H3L complexes under the MALDI conditions
or insufficient desorption.)30 The initial solubility of
coordination polymers was good in chloroform/methanol,
but they slowly started to precipitate within 1 day after
preparation, which suggested that the polymers were
consolidating, thereby increasing their molecular weight.22b
The fluorescence titration experiment showed the
fluorescence quenching of perylene bisimide in the pres-
ence of FeIII (Figure 5). In particular, upon addition of
FeIII to the solution of 4 in 1:2 ratio, the fluorescence of
perylene almost quenched completely, which indicated
the formation of dimeric complex. Similar results were
obtained for 7b-FeIII complex. According to these UV-
Electrochemical Properties of Perylene Bisimide
Ligand-Metal Complexes. The electrochemical prop-
erties of the polymers and model compounds were also
studied. The representative cyclic voltammograms were
shown in Figure 6. In the cathodic scans, 4b, 7b exhibited
quasireversible reduction waves at E1/2 values of -0.98
and -1.12 V; 7b-Fe showed a wave at -0.89 V. These
waves were attributed to the reduction of perylene
bisimide moieties. In the anodic scans, oxidation peak of
4b at 1.05 V was observed. 7b showed an irreversible
wave at 1.12 V, wehreas when complexed with Fe, a more
negative oxidation peak at 1.05 V appeared. These data
showed that the electrochemical properties of the Fe-
complexed perylene bisimide ligands were improved
compared with that of noncomplexed ligands: their
energy gaps between the highest occupied molecular
orbital (HOMO) and the lowest occupied molecular
orbital (LOMO) decreased (Table 2). It is clear that the
spacer unit R (rigid phenylene group, flexible -CH2-
(30) Schmatloch, S.; van den Berg, A. M. J.; Alexeev, A. S.; Hofmeier,
H.; Schubert, U. S. Macromolecules 2003, 36, 9943.
J. Org. Chem, Vol. 70, No. 24, 2005 9689

Li et al.
FIGURE 7. Scanning electron micrograph (SEM) images of self-assembled 7a-Fe (a), 7b-Fe (b), and 7c-Fe (c) coordination polymers
in CHCl3.
TABLE 2. Electrochemical Properties of Perylene
Bisimide Ligand and Fe(III) Complexes
Conclusion
In conclusion, new perylene bisimide dyes connected
with 3,5-bis(2-hydroxyphenyl)-1,2,4-triazole (H3L) recep-
tor units through different spacers have been synthesized
and characterized successfully. The spacer between the
H3L ligands and the perylene bisimide affected the
fluorescence of the core perylene bisimide, and this sort
of compound can be used as good red emission materials.
MALDI-TOF mass spectrometry, UV-vis spectroscopy,
and fluorescence titration experiments proved that mono-
topic perylene bisimide ligands could be assembled to
nonfluorescent dimmers by FeIII ion coordination. The
coordination properties of the ditopic perylene bisimide
ligands have also been investigated preliminarily, and
the study of the polymer structure is underway. The
electrochemical studies showed that the electronic prop-
erties of those with flexible -CH2- linkages are similar;
in contrast, those with rigid phenylene linkages became
easier to reduce but more difficult to oxidize. The band
gaps of the Fe-complexed perylene bisimide ligands
decreased compared with those of noncomplexed ligands.
Furthermore, the SEM images indicated that well-
defined nanoscale structures could be fabricated by self-
assembly due to metal ion coordination and π-π stacking
interactions of perylene rings with the help of a proper
spacer.
oxidation
reduction
E1/2
E1/2 (1)
E1/2 (2)
band gap (eV)a
4a
1.08
1.05
1.36
1.13
1.12
1.31
1.02
1.03
1.05
1.14
-0.98
-0.98
-0.80
-0.99
-0.98
-0.81
-0.91
-0.85
-0.89
-0.72
-1.11
-1.12
-0.95
-1.09
-1.12
-0.94
1.85
1.84
1.95
1.83
1.83
1.93
1.64
1.62
1.65
1.57
4b
4c
7a
7b
7c
4b + Fe
7a + Fe
7b + Fe
7c + Fe
a Gained from the Eonset
.
linkages) have evident influence on the electrical proper-
ties of these compounds in the ground state. Both
compounds with flexible -CH2- linkages exhibit nodes at
the imide N atoms,31 which indicate that the substituents
at those positions do not influence the energy levels of
the compounds, so the electronic properties of those with
flexible -CH2- linkages, no matter long or short, are
similar. In contrast, those with rigid phenylene linkages
became easier to reduce but more difficult to oxidize.
SEM Images of Perylene Bisimide Ligand-Metal
Complexes. It was clear that the spacer unit R (rigid
phenylene group, flexible -CH2- linkages) had evident
influence on the optical and electrical properties in the
ground state and great influence on the nanostructure
of these self-assembling photofunctional materials. Fig-
ure 7 showed the scanning electron micrograph (SEM)
images of self-assembled 7a-Fe, 7b-Fe, and 7c-Fe coor-
dination structures in CHCl3. From the electron micro-
graph images in Figure 7 it was sure that 7a-Fe tended
to form capsule-like structures with diameters in the
range of 200-300 nm (arrows indicate the broken ones),
7b-Fe formed one-dimensional ball-like supramolecular
structures with diameters around 50 nm, and 7c-Fe self-
assembled aggregates tend to form rod-like supra-
molecular structures with diameters in the range of 50-
100 nm, whose lengths were extended to 1-2 µm and
which tended to aggregate into bigger rods. These ag-
gregates mainly resulted from the π-π stacking interac-
tions of perylene rings, and the spacers between the
ligands and perylene bisimide affected the aggregates
structures.
Experimental Section
N,N′-Dioctyl-1,6,7,12-tetra(4-tert-butylphenoxy)-peryl-
ene-3,4,9,10-tetracarboxylic Diimide (1). Prepared from
1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic acid bis-
anhydride according to literature25b but with octylamine. H
1
NMR (400 M, CDCl3, TMS), δ 8.22(s, 4 H), 7.22(d, 8 H), 6.82(d,
8 H), 4.10(t, 4 H), 1.66(m, 4 H), 1.36(m, 4 H), 1.29(s, 44 H),
0.86(t, 6 H). IR spectrum (KBr) ν ) 3057, 2959, 2927, 2861,
1697, 1660, 1589, 1504, 1410, 1349, 1289, 1218, 1173, 1112,
1018, 881, 838, 733, 554 cm-1. MALDI-TOF calcd 1206.7, obsd
1221.7. Anal. Calcd for C80H90N2O8: C, 79.57; H, 7.51; N, 2.32.
Found: C, 79.02; H, 7.57; N, 2.19.
N-Octyl-1,6,7,12-tetra(4-tert-butylphenoxy)-perylene-
3,4-anhydride-9,10-tetracarboxylic Imide (2) and 1,6,7,12-
Tetra(4-tert-butylphenoxy)-perylene-3,4,9,10-tetracar-
boxylic Bisanhydride (5). N,N′-Dioctyl-1,6,7,12-tetra(4-tert-
butylphenoxy)-perylene-3,4,9,10-tetracarboxylic diimide (3.6 g,
3.0 mmol) with KOH (6 g, 10 mmol) in isopropyl alcohol (60
mL) and H2O (3 mL) under argon by stirring at reflux for 10
h, followed by acidic workup and thorough washing and drying,
yielded a mixture (3.0 g) of perylene bisanhydride (5) and
perylene mono octylimide (2) in a ratio of about 7:3. 2 and 5
were separated by column chromatography on a silica gel with
CH2Cl2/petroleum ether (1:2).
(31) Langhals, H.; Demmig, S.; Huber, H. Spectrochim. Acta, Part
A 1988, 44A, 1189.
9690 J. Org. Chem., Vol. 70, No. 24, 2005

Synthesis of Functionalized Perylene Bisimides
N-Octyl-N′-(8-aminooctyl)-1,6,7,12-tetra(4-tert-butyl-
phenoxy)-perylene-3,4,9,10-tetracarboxylic Diimide (3a).
Perylene monooctylimide 2 (0.28 g, 0.25 mmol), 1,8-diamino-
octane (0.36 g, 2.5 mmol), and imidazole(100 mg) were stirred
under argon at reflux for 0.5 h in toluene (80 mL). The reaction
mixture was washed with water twice and then dried over
anhydrous sodium sulfate. The solvent was removed in vacuo.
Purification was carried out by column chromatography on a
silica gel with CHCl3 as eluent, affording 3a (0.21 g, 70% yield).
1H NMR (400 M, CDCl3, TMS), δ 8.22 (s, 4 H), 7.23 (d, 8 H, J
) 8.0 Hz), 6.82 (d, 8 H, J ) 8.0 Hz), 4.09 (t, 4 H, J ) 7.1 Hz),
2.67 (t, 2 H, J ) 6.9 Hz), 2.0 (br, -NH2), 1.66 (m, 4 H), 1.42
(m, 2 H), 1.29 (m, 54 H), 0.85 (t, 3 H, J ) 6.7 Hz). IR spectrum
(KBr) ν ) 3041, 2959, 2928, 2859, 1698, 1661, 1590, 1504,
1436, 1411, 1351, 1286, 1216, 1173, 1111, 1016, 879, 837, 554
cm-1. UV-vis (CHCl3): λmax/nm ) 584, 543, 453. MALDI-TOF
calcd 1222.6, obsd 1221.7. Anal. Calcd for C80H91N3O8: C,
78.59; H, 7.50; N, 3.44. Found: C, 78.51; H, 7.48; N, 3.49.
(s, 4 H), 7.03 (d, 8 H, J ) 8.7 Hz), 6.82 (d, 8 H, J ) 8.7 Hz),
4.21 (t, 4 H, J ) 6.4 Hz), 3.01 (t, 4 H, J ) 6.4 Hz), 1.29 (s, 36
H). IR spectrum (KBr) ν ) 3389, 3041, 2960, 2867, 1699, 1662,
1589, 1504, 1434, 1410, 1347, 1285, 1215, 1174, 1109, 1016,
878, 836, 803, 554 cm-1
. UV-vis (CHCl3): λmax/nm ) 586, 543,
455. MALDI-TOF calcd 1069.2, obsd 1068.8. Anal. Calcd for
C68H68N4O8: C, 76.38; H, 6.41; N, 5.24. Found: C, 76.03; H,
6.37; N, 5.19.
N,N′-Di(4-aminophenyl)-1,6,7,12-tetra(4-tert-butylphe-
noxy)-perylene-3,4,9,10-tetracarboxylic Diimide (6c).
Perylene bisanhydride 5 (0.50 g, 0.5 mmol), benzene-1,4-
diamine (0.54 g, 5 mmol), and imidazole (200 mg) were allowed
to react in the same way as described for 6a and purified by
column separation (silica gel, CH2Cl2) to yield 6c (435 mg,
1
75%). H NMR (400 M, CDCl3, TMS), δ 8.23 (s, 4 H), 7.22 (d,
8 H, J ) 8.7 Hz), 7.00 (d, 4 H, J ) 8.5 Hz), 6.83 (d, 8 H, J )
8.6 Hz), 6.76 (d, 4 H, J ) 8.5 Hz), 1.60 (br, -NH2), 1.26 (s, 36
H). IR spectrum (KBr) ν ) 3377, 3042, 1702, 1667, 1587, 1507,
1407, 1341, 1286, 1208, 1174, 881, 834, 553 cm-1. UV-vis
(CHCl3): λmax/nm ) 584, 545, 453. MALDI-TOF calcd 1165.3,
obsd 1164.2. Anal. Calcd for C76H68N4O8: C, 78.33; H, 5.88;
N, 4.81. Found: C, 78.17; H, 5.81; N, 4.74.
N-Octyl-N′-(2-aminoethyl)-1,6,7,12-tetra(4-tert-butyl-
phenoxy)-perylene-3,4,9,10-tetracarboxylic Diimide (3b).
Perylene monooctylimide 2 (0.28 g, 0.25 mmol), 1,2-ethylene-
diamine (0.075 g, 2.5 mmol), and imidazole (100 mg) were
allowed to react in the same way as described for 3a and
purified by column separation (silica gel, chloroform) to yield
3b (213 mg, 75%). 1H NMR (400 M, CDCl3, TMS), δ 8.22 (s, 2
H), 8.21 (s, 2 H), 7.22 (d, 8 H, J ) 8.7 Hz), 6.82 (dd, 8 H, 2.3
Hz, 8.3 Hz), 4.5 (br, -NH2), 4.23 (t, 2 H, J ) 6.2 Hz), 4.09 (t,
2 H, J ) 7.0 Hz), 3.04 (t, 2 H, J ) 6.0 Hz), 1.66 (m, 2 H), 1.28
(m, 46 H), 0.84 (t, 3 H, J ) 6.2 Hz). IR spectrum (KBr) ν )
3375, 3062, 2960, 2868, 1699, 1662, 1589, 1504, 1434.8, 1411,
Ligand Derivative 4a. 4-[3,5-Bis(2-hydroxyphenyl)-1,2,4-
triazol-1-yl] benzoyl chloride (0.2 mmol) and N-octyl-N′-(8-
aminooctyl)-1,6,7,12-tetra(4-tert-butylphenoxy)-perylene-3,4,9,10-
tetracarboxylic diimide (3a) (122 mg, 0.10 mmol) were allowed
to react according to the general procedure and purified by
column separation (silica gel, CH2Cl2) to yield a black powder
1
(55 mg, 35%). H NMR (400 M, CDCl3, TMS), δ 8.21 (s, 4 H),
8.12 (dd, 1 H, J ) 7.8 Hz, 1.5 Hz), 7.93 (d, 2 H, J ) 8.5 Hz),
7.57 (d, 2 H, J ) 8.5 Hz), 7.37-7.30 (m, 2 H), 7.22 (d, 8 H, J
) 8.7 Hz), 7.12 (d, 1 H, J ) 8.4 Hz), 7.05 (m, 2 H), 6.91 (dd, 1
H, J ) 8.0 Hz, 1.4 Hz), 6.82 (d, 8 H, J ) 8.6 Hz), 6.64 (t, 1 H,
J ) 7.2 Hz, 8.1 Hz), 6.17 (t, 1 H, J ) 5.0 Hz, 5.7 Hz), 4.10 (m,
4 H), 3.48 (m, 2 H), 1.66 (m, 6 H), 1.36 (m, 10 H), 1.28 (s, 36
H), 1.25 (m, 8 H), 0.84 (t, 3 H, J ) 7.0 Hz). 13C NMR (100 M,
CDCl3, TMS), δ165.9, 163.3, 159.4, 157.9, 156.3, 155.8, 155.7,
152.7, 151.9, 147.1, 140.1, 136.3, 132.8, 132.7, 132.7, 131.6,
128.5, 127.5, 127.4, 126.5, 126.1, 122.4, 122.2, 120.4, 120.3,
119.7, 119.3, 119.2, 118.9, 118.3, 116.9, 113.0, 109.7, 40.5, 40.4,
40.2, 34.2, 31.6, 31.3, 29.4, 29.1, 29.0, 28.9, 27.9, 27.8, 27.0,
26.8, 26.7, 22.5, 13.9. IR spectrum (KBr) ν ) 3306, 3062, 2958,
2860, 1698, 1660, 1589, 1504, 1463, 1411, 1351, 1285, 1215,
1347, 1286, 1216, 1174, 1112, 1016, 880, 837, 754, 555 cm-1
.
UV-vis (CHCl3): λmax/nm ) 587, 547, 459. MALDI-TOF calcd
1138.4, obsd 1137.7. Anal. Calcd for C74H79N3O8: C, 78.07; H,
6.99; N, 3.69. Found: C, 77.95; H, 6.92; N, 3.63.
N-Octyl-N′-(4-aminophenyl)-1,6,7,12-tetra(4-tert-butyl-
phenoxy)-perylene-3,4,9,10-tetracarboxylic Diimide (3c).
Perylene mono octylimide 2 (0.28 g, 0.25 mmol), benzene-1,4-
diamine (0.27 g, 2.5 mmol), and imidazole (100 mg) were
allowed to react in the same way as described for 3a and
purified by column separation (silica gel, CH2Cl2) to yield 3c
(228 mg, 77%). 1H NMR (400 M, CDCl3, TMS), δ8.23 (s, 2 H),
8.21 (s, 2 H), 7.22 (m, 8 H), 7.10 (d, 2 H, J ) 8.3 Hz), 7.04 (m,
2 H), 6.83 (m, 8 H), 4.10 (t, 2 H, J ) 7.0 Hz), 1.66 (m, 2 H),
1.33 (m, 2 H), 1.26 (s, 44 H), 0.85 (t, 3 H, J ) 6.7 Hz). IR
spectrum (KBr) ν ) 3374, 3041, 2958, 2864, 1699, 1663, 1588,
1505, 1409, 1341, 1287, 1213, 173, 1109, 1014, 833, 731, 552
cm-1. UV-vis (CHCl3): λmax/nm ) 584, 541, 453. MALDI-TOF
calcd 1186.5, Observed, 1185.3. Anal. Calcd for C78H79N3O8:
C, 78.96; H, 6.71; N, 3.54. Found: C, 78.75; H, 6.67; N 3.48.
1171, 1111, 1016, 836, 754, 554 cm-1. UV-vis (CHCl3): λmax
/
nm (ꢀ/L mol-1 cm-1) ) 585 (46650), 545 (28030), 454 (17100),
287 (63460). Fluorescence (CHCl3): λmax/nm ) 623.1, fluores-
cence quantum yield (λexe ) 550 nm, E550nm ) 0.0414/1 cm,
CHCl3, reference N,N′-bis(2,6-diisopropylphenyl)-1,6,7,12-tetra-
phenoxyperylene-3,4,9,10-tetracarboxylic diimide (TPPI) with
Φ ) 0.96 in CHCl3) ) 0.91. MALDI-TOF calcd 1577.9, obsd
1577.9. Anal. Calcd for C101H104N6O11: C, 76.88; H, 6.64; N,
5.33. Found: C, 76.53; H, 6.58; N, 5.41.
N,N′-Di(8-aminooctyl)-1,6,7,12-tetra(4-tert-butylphe-
noxy)-perylene-3,4,9,10-tetracarboxylic Diimide (6a).
Perylene bisanhydride 5 (0.50 g, 0.5 mmol), 1,8-diaminooctane
(0.72 g, 5 mmol), and imidazole (200 mg) were stirred under
argon at reflux for 0.5 h in toluene (80 mL). The reaction
mixture was washed with water twice and then dried over
anhydrous sodium sulfate. The solvent was removed in vacuo.
Purification was carried out by column chromatography on a
silica gel with CHCl3/methanol (10:1) as eluent, affording 6a
Ligand Derivative 4b. 4-[3,5-Bis(2-hydroxyphenyl)-1,2,4-
triazol-1-yl] benzoyl chloride (0.2 mmol) and N-octyl-N′-(2-
aminoethyl)-1,6,7,12-tetra(4-tert-butylphenoxy)-perylene-
3,4,9,10-tetracarboxylic diimide (3b) (113 mg, 0.10 mmol) were
allowed to react according to the general procedure and
purified by column separation (silica gel, CH2Cl2) to yield a
black powder (60 mg, 40%). 1H NMR (300 M, CDCl3, TMS), δ
9.50 (bs, 1 H), 8.27 (s, 2 H), 8.20 (s, 2 H), 8.14 (dd, 1 H, J )
8.1 Hz, 1.4 Hz), 7.90 (d, 2 H, J ) 8.4 Hz), 7.51 (d, 2 H, J ) 8.3
Hz), 7.39 (m, 1 H), 7.20 (m, 8 H), 7.15-7.02 (m, 3 H), 6.86 (dd,
1 H, J ) 8.0 Hz, 1.2 Hz), 6.80 (dd, 8 H, J ) 8.7 Hz, 2.0 Hz),
6.60 (m, 1 H), 4.52 (m, 2 H), 4.09 (m, 2 H), 3.90 (m, 2 H), 1.66
(m, 2 H), 1.32 (m, 2 H), 1.28 (s, 18 H), 1.25 (m, 8 H), 1.23 (s,
18 H), 0.84 (m, 3 H). 13C NMR (100 M, CDCl3, TMS), δ 166.0,
164.4, 163.3, 159.4, 158.0, 156.5, 156.3, 155.7, 152.9, 152.6,
152.1, 147.4, 147.3, 140.2, 135.8, 132.9, 132.7, 131.8, 128.7,
127.6, 127.4, 126.7, 126.6, 126.2, 122.7, 121.6, 121.4, 120.4,
119.9, 119.8, 119.6, 119.4, 119.2, 119.1, 119.0, 118.3, 117.1,
113.1, 109.8, 40.7, 40.6, 39.5, 34.3, 34.2, 31.7, 31.4, 31.3, 29.2,
29.1, 28.1, 27.1, 22.6, 14.0. IR spectrum (KBr) ν ) 3351, 3062,
1
(0.42 g, 68% yield). H NMR (400 M, CDCl3, TMS), δ 8.21 (s,
4 H), 7.22 (d, 8 H, J ) 8.1 Hz), 6.82 (d, 8 H, J ) 8.0 Hz), 4.08
(m, 4 H), 2.66 (t, 4 H, J ) 6.6 Hz), 1.80 (br, -NH2), 1.65 (m, 8
H), 1.29 (m, 52 H). UV-vis (CHCl3): λmax/nm ) 585, 542, 454.
MALDI-TOF calcd 1237.6, obsd 1237.1. Anal. Calcd for
C80H92N4O8: C, 77.64; H, 7.49; N, 4.53. Found: C, 76.98; H,
7.44; N, 4.50.
N,N′-Di(2-aminoethyl)-1,6,7,12-tetra(4-tert-butylphe-
noxy)-perylene-3,4,9,10-tetracarboxylic Diimide (6b).
Perylene bisanhydride 5 (0.50 g, 0.5 mmol), 1,2-ethylenedi-
amine (0.15 g, 5 mmol), and imidazole (200 mg) were allowed
to react in the same way as described for 6a and purified by
column separation (silica gel, chloroform/methanol 10:1) to
yield 6b (345 mg, 65%). 1H NMR (400 M, CDCl3, TMS), δ 8.22
J. Org. Chem, Vol. 70, No. 24, 2005 9691

Li et al.
2959, 2865, 1698, 1662, 1589, 1503, 1411, 1347, 1286, 1216,
1173, 1112, 1019, 836, 754, 554 cm-1. UV-vis (CHCl3): λmax
black powder (64 mg, 36%). 1H NMR (400 M, CDCl3, TMS), δ
9.61(sb, 2 H), 8.23 (s, 4 H), 8.12 (m, 2 H), 7.88 (d, 4 H, J ) 8.4
Hz), 7.57 (s, 1 H), 7.49 (d, 4 H, J ) 8.4 Hz), 7.38 (m, 2 H), 7.22
(m, 2 H), 7.17 (d, 8 H, J ) 8.6 Hz), 7.15∼6.99 (m, 8 H), 6.85
(m, 2 H), 6.77 (d, 8 H, J ) 8.7 Hz), 6.56 (t, 2 H, J ) 7.7 Hz),
4.51 (m, 4 H), 3.87 (m, 4 H), 1.22 (s, 36 H). 13C NMR (100 M,
CDCl3, TMS), δ 166.1, 164.2, 159.4, 158.0, 156.4, 156.0, 152.7,
152.0, 147.5, 140.2, 135.8, 132.9, 132.8, 131.8, 128.7, 127.6,
127.4, 126.7, 126.1, 121.9, 120.8, 120.2, 119.8, 119.4, 119.2,
119.0, 118.3, 117.1, 113.1, 109.8, 40.4, 39.6, 34.3, 31.5. IR
spectrum (KBr) ν ) 3301, 3060, 2960, 2868, 1699, 1662, 1588,
1503, 1464, 1410, 1348, 1288, 1215, 1173, 1111, 1016, 835, 753,
553 cm-1. UV-vis (CHCl3): λmax/nm (ꢀ/L mol-1 cm-1) ) 589
(47900), 548 (28840), 457 (17900), 288 (59970). Fluorescence
/
nm (ꢀ/L mol-1 cm-1) ) 593 (44320), 553 (27280), 459 (16480),
293 (67670). Fluorescence (CHCl3): λmax/nm ) 617.6, fluores-
cence quantum yield (λexe ) 550 nm, E550nm ) 0.0414/1 cm,
CHCl3, reference TPPI with Φ ) 0.96) ) 0.81. MALDI-TOF
calcd 1493.8, obsd 1492.7. Anal. Calcd for C95H92N6O11: C,
76.38; H, 6.21; N, 5.63. Found: C, 76.19; H, 6.17; N, 5.69.
Ligand Derivative 4c. 4-[3,5-Bis(2-hydroxyphenyl)-1,2,4-
triazol-1-yl] benzoyl chloride (0.2 mmol) and N-octyl-N′-(4-
aminophenyl)-1,6,7,12-tetra(4-tert-butylphenoxy)-perylene-
3,4,9,10-tetracarboxylic diimide (3c) (119 mg, 0.10 mmol) were
allowed to react according to the general procedure except in
THF and purified by column separation (silica gel, CH2Cl2) to
1
yield a black powder (49 mg, 32%). H NMR (400 M, CDCl3,
(CHCl3): λmax/nm ) 620.3, fluorescence quantum yield (λexe )
TMS), δ 8.24 (s, 2 H), 8.22 (s, 2 H), 8.12 (s, 1 H), 8.10 (dd, 1 H,
J ) 7.8 Hz, 1.5 Hz), 8.06 (d, 2 H, J ) 8.5 Hz), 7.79 (d, 2 H, J
) 8.7 Hz), 7.61 (d, 2 H, J ) 8.5 Hz), 7.32 (m, 2 H), 7.25-7.20
(m, 10 H), 7.12 (d, 1 H, J ) 8.3 Hz), 7.0 (m, 2 H), 6.93 (dd, 1
H, J ) 6.0 Hz, 1.4 Hz), 6.86 (m, 8 H), 6.66 (t, 1 H, J ) 7.2 Hz),
4.11 (t, 2 H, J ) 7.7 Hz), 1.66 (m, 2 H), 1.34 (m, 2 H), 1.29 (s,
20 H), 1.25 (s, 24 H), 0.85 (m, 3 H). 13C NMR (100 M, CDCl3,
TMS), δ 164.5, 163.8, 163.7, 163.4, 159.5, 158.0, 156.3, 156.1,
155.9, 152.8, 152.2, 147.4, 140.6, 138.0, 136.3, 133.0, 131.6,
131.5, 129.2, 129.0, 127.6, 127.5, 126.7, 126.7, 126.4, 122.7,
122.1, 120.3, 120.1, 119.8, 119.7, 119.3, 119.1, 118.4, 116.9,
112.9, 109.9, 34.3, 31.8, 31.5, 31.2, 29.3, 29.1, 28.1, 27.1, 22.6,
14.1. IR spectrum (KBr) ν ) 3293, 3061, 2958, 2863, 1702,
1665, 1589, 1505, 1409, 1343, 1285, 1211, 1173, 1108, 1015,
550 nm, E550nm ) 0.0369/1 cm, CHCl3, reference TPPI with Φ
) 0.96) ) 0.75. MALDI-TOF calcd 1779.9, obsd 1778.9. Anal.
Calcd for C110 H94N10O14: C, 74.22; H, 5.32; N, 7.87. Found:
C, 74.02; H, 5.28; N, 7.59.
Ligand Derivative 7c. 4-[3,5-Bis(2-hydroxyphenyl)-1,2,4-
triazol-1-yl] benzoyl chloride (0.4 mmol) and N,N′-di(4-amino-
phenyl)-1,6,7,12-tetra(4-tert-butylphenoxy)-perylene-3,4,9,10-tetra-
carboxylic diimide (6c) (116 mg, 0.10 mmol) were allowed to
react according to the general procedure except in THF and
purified by column separation (silica gel, CH2Cl2) to yield a
black powder (56 mg, 30%). 1H NMR (400 M, d6-DMSO, TMS),
δ 10.80(s, 2 H), 10.49 (s, 2 H), 10.10 (s, 2 H), 8.08∼8.04 (m, 8
H), 7.93 (s, 4 H), 7.86 (d, 4 H, J ) 8.56 Hz), 7.61 (d, 4 H, J )
8.56 Hz), 7.56 (d, 4 H, J ) 7.76 Hz), 7.43∼7.37 (m, 4 H),
7.32∼7.28 (m, 8 H), 7.05∼7.00 (m, 6 H), 6.91∼6.84 (m, 10 H),
1.23 (s, 36 H). 13C NMR could not be recorded because of the
low solubility of the compound; IR spectrum (KBr) ν ) 3306,
3063, 1706, 1672, 1589, 1509, 1465, 1408, 1341, 1289, 1209,
1175, 1102, 802, 755, 556 cm-1. UV-vis (CHCl3): λmax/nm (ꢀ/L
mol-1 cm-1) ) 587 (51060), 546 (30640), 456 (17400), 289
(75050). Fluorescence (CHCl3): λmax/nm ) 615.2, fluorescence
quantum yield (λexe ) 550 nm, E550nm ) 0.0343/1 cm, CHCl3,
reference TPPI with Φ ) 0.96) ) 0.90. MALDI-TOF calcd
1876.1, obsd 1874.5. Anal. Calcd for C118H94N10O14: C, 75.54;
H, 5.05; N, 7.47. Found: C, 75.43; H, 5.12; N, 7.55.
831, 754, 554 cm-1. UV-vis (CHCl3): λmax/nm (ꢀ/L mol-1 cm-1
)
) 589 (41160), 548 (24820), 459 (13320), 296 (75060). Fluo-
rescence (CHCl3): λmax/nm ) 614.4, fluorescence quantum yield
(λexe ) 550 nm, E550 nm ) 0.0460/1 cm, CHCl3, reference TPPI
with Φ ) 0.96) ) 0.88. MALDI-TOF calcd 1541.8, obsd 1540.6.
Anal. Calcd for C99 H92N6O11: C, 77.12; H, 6.01; N, 5.45.
Found: C, 76.98; H, 6.09; N, 5.61.
Ligand Derivative 7a. 4-[3,5-Bis(2-hydroxyphenyl)-1,2,4-
triazol-1-yl] benzoyl chloride (0.4 mmol) and N,N′-di(8-amino-
octyl)-1,6,7,12-tetra(4-tert-butylphenoxy)-perylene-3,4,9,10-tetra-
carboxylic diimide (6a) (123 mg, 0.10 mmol) were allowed to
react according to the general procedure and purified by
column separation (silica gel, CH2Cl2/CH3OH 10:1) to yield a
black powder (78 mg, 40%). 1H NMR (300 M, CDCl3, TMS), δ
11.5 (sb, 2 H), 9.57 (sb, 2 H), 8.21 (s, 4 H), 8.12 (d, 2 H, J )
7.6 Hz), 7.93 (d, 4 H, J ) 8.3 Hz), 7.57 (d, 4 H, J ) 8.4 Hz),
7.32 (m, 4 H), 7.22 (d, 8 H, J ) 8.7 Hz), 7.12 (d, 2 H, J ) 8.3
Hz), 7.05 (m, 4 H), 6.91 (d, 2 H, J ) 7.7 Hz), 6.80 (d, 8 H, J )
8.7 Hz), 6.64 (t, 2 H, J ) 7.6 Hz, 7.7 Hz), 6.20 (t, 2 H, J ) 5.0
Hz, 5.1 Hz), 4.11 (m, 4 H), 3.47 (m, 4 H), 1.65 (m, 8 H), 1.36
(m, 16 H), 1.28 (s, 36 H). 13C NMR (100 M, CDCl3, TMS), δ
166.1, 163.4, 159.5, 157.9, 156.4, 155.9, 152.9, 152.0, 147.3,
140.2, 136.3, 132.9, 132.8, 131.8, 128.6, 127.6, 127.6, 126.6,
126.1, 122.4, 120.5, 119.8, 119.4, 119.3, 119.1, 118.3, 117.1,
113.1, 110.0, 0.6, 40.4, 34.4, 31.5, 29.5, 29.1, 27.9, 27.0, 26.9.
IR spectrum (KBr) ν ) 3288, 3062, 2957, 28608, 1696, 1657,
1588, 1503, 1463, 1410.3, 1351, 1286, 1214, 1170, 1109, 1015,
4a + Fe + 4a. UV-vis (CHCl3): λmax/nm (ꢀ/L mol-1 cm-1
)
) 585 (93000), 545 (56100), 454 (34000). IR spectrum (KBr) ν
) 2959, 2861, 1697, 1659, 1590, 1504, 1462, 1438, 1411, 1350,
1287, 1216, 1172, 1110, 1016, 843, 755, 554 cm-1. MALDI-
TOF: 3207.5[4a + Fe + 4a]-, 1631.6[4a + Fe]-, 1577.8[4a]-.
4b + Fe + 4b. UV-vis (CHCl3): λmax/nm (ꢀ/L mol-1 cm-1
)
) 589 (89100), 548 (54000), 458 (32000). IR spectrum (KBr) ν
) 2959, 2865, 1697, 1661, 1589, 1503, 1463, 1435, 1410, 1346,
1287, 1216, 1172, 1111, 1016, 838, 754, 553 cm-1. MALDI-
TOF: 3039.1[4b + Fe + 4b]-, 1547.7[4b + Fe]-, 1493.8[4b]-.
4c + Fe + 4c. UV-vis (CHCl3): λmax/nm (ꢀ/L mol-1 cm-1) )
587 (90300), 545 (56000), 457 (314000). IR spectrum (KBr) ν
) 2958, 2864, 1701, 1664, 1591, 1506, 1462, 1408, 1342, 1284,
1212, 1172, 1108, 1015, 834, 755, 553 cm-1. MALDI-TOF:
3135.4[4c + Fe + 4c]-, 1594.5[4c + Fe]-, 1540.6[4c]-.
835, 754, 554 cm-1. UV-vis (CHCl3): λmax/nm (ꢀ/L mol-1 cm-1
) 585 (46650), 545 (28030), 454 (17100). Fluorescence
(CHCl3): λmax/nm ) 614.4, fluorescence quantum yield (λexe
)
Acknowledgment. This work was supported by
the Major State Basic Research development Pro-
gram and the National Natural Science Foundation of
China (20131040, 50372070, 20418001, 20473102 and
20421101).
)
5 50 nm, E550nm ) 0.0414/1 cm, CHCl3, reference TPPI with Φ
) 0.96) ) 0.88. MALDI-TOF calcd 1948.3, obsd 1948.6. Anal.
Calcd for C122 H118N10O14: C, 75.21; H, 6.10; N, 7.19. Found:
C, 74.75; H, 5.94; N, 7.21.
Ligand Derivative 7b. 4-[3,5-Bis(2-hydroxyphenyl)-1,2,4-
triazol-1-yl] benzoyl chloride (0.4 mmol) and N,N′-di(2-amino-
ethyl)-1,6,7,12-tetra(4-tert-butylphenoxy)-perylene-3,4,9,10-tetra-
carboxylic diimide (6b) (107 mg, 0.10 mmol) were allowed to
react according to the general procedure and purified by
column separation (silica gel, CH2Cl2/CH3OH 50:1) to yield a
Supporting Information Available: General experimen-
tal methods and spectral data (1HNMR,13CNMR) for new
compounds. This material is available free of charge via the
Internet at http://pubs.acs.org.
JO051022C
9692 J. Org. Chem., Vol. 70, No. 24, 2005