Benzothiadiazoloperylenes and benzoxadiazoloperylenes: Amorphous functional materials

Article abstract of DOI:10.1055/s-0032-1316785

2,1,3-Benzothiadiazole or 2,1,3-benzoxadiazole were magnesiated (TMP ₂Mg·2LiCl) and efficiently attached to perylene and benzoperylene building blocks providing amorphous light-absorbing materials where FRET energy transfer proceeds between the

Full text of DOI:10.1055/s-0032-1316785

PAPER
▌3465
paper
Benzothiadiazoloperylenes and Benzoxadiazoloperylenes:
Amorphous Functional Materials
Benzothiadiazoloperylenes and Benzoxadiazoloperylenes
Heinz Langhals,* Paul Knochel,* Andreas Walter, Silvia Zimdars
Department of Chemistry, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, Haus F, 81377 München, Germany
Fax +49(89)218077640; E-mail: Langhals@lrz.uni-muenchen.de; Fax +49(89)218077680; E-mail: Paul.Knochel@cup.uni-muenchen.de
Received: 23.08.2012; Accepted after revision: 27.08.2012
tries 3 and 4). Cross-coupling of 4-iodoaniline, 5-iodopyr-
Abstract: 2,1,3-Benzothiadiazole or 2,1,3-benzoxadiazole were
idin-2-amine, or 3-iodoaniline allowed the preparation of
magnesiated (TMP2Mg·2LiCl) and efficiently attached to perylene
the amino derivatives 3c–f and 4a,b, respectively, with
amino groups for the condensation with carboxylic anhy-
and benzoperylene building blocks providing amorphous light-
absorbing materials where FRET energy transfer proceeds between
the 2,1,3-benzothiadiazole or 2,1,3-benzoxadiazole and the per- drides (entries 5–8, 1 and 2). Finally, 3g was prepared
ylene units. Some of these new materials were obtained as amor-
phous solids of interest for material science.
from 1-iodo-4-(trimethylsilyl)benzene and was further
converted into 3h by means of iodine monochloride to be-
Key words: arenes, heterocycles, imides, cross-coupling fused-
ring systems, zinc
come the starting material for subsequent cross-coupling
reactions (entries 9 and 10).
Y
Y
Organic functional materials with special electronic and
optical properties are of increasing interest in science and
technology;1 their variability and saving of resources are
important features. Organic light emitting diodes
(OLEDS) and organic photovoltaic devices based on ex-
tended π-systems of polycyclic aromatic or heteroaromat-
ic compounds are very promising and much research
activity is focused on perylenetetracarboxylic bisimides2,3
because of their high chemical and photochemical stabili-
ty.4,5 However, their tendency for crystallization is prob-
lematic for such functional materials, since the molecular
packing invariably determined by the crystal lattice is
Y
N
N
N
N
N
N
ii
i
ZnCl
Z
X
1a Y = S
1b Y = O
2a Y = S
2b Y = O
3
ii
Y
N
N
NH2
4
hard to predict and cannot be continuously altered. More- Scheme 1 Synthesis of 2,1,3-benzothiadiazoles and 2,1,3-benzoxa-
diazoles, respectively. Reagents and conditions: (i) 1.
(TMP)2Mg·2LiCl, THF; 2. ZnCl2; (ii) see Table 1.
over, there are interfering border effects between the crys-
tallites. The availability of amorphous organic materials6
would solve these problems. Herein, we wish to report the
synthesis of such new amorphous materials bearing a per-
ylene or benzoperylene moiety attached to 2,1,3-benzo-
thiadiazole and 2,1,3-benzoxadiazole units, respectively,
as well as their interesting optical properties.
The amino derivatives 3c–f were condensed with the per-
ylene anhydride carboximides 5a and 5b to form the per-
ylenetetracarboxylic bisimides 6a,e and 7a where the
long-chain secondary alkyl substituents increases the sol-
ubility of the materials and 1-nonyldecyl is more efficient
than the 1-hexylheptyl substituent (Scheme 2, Table 2).
We started the synthesis with 2,1,3-benzothiadiazole (1a)
and 2,1,3-benzoxadiazole (1b) and prepared the novel
zinc reagents 2a and 2b,7 respectively, by direct magnesi-
ation with bis(2,2,6,6-tetramethylpiperidin-1-yl)magne-
sium–lithium chloride complex8 (TMP2Mg·2LiCl) in
tetrahydrofuran (1.4 equiv, –40 °C or –5 °C, 14 h) fol-
lowed by transmetalation with zinc chloride (1.5 equiv,
–40 °C or –5 °C, 0.5 h) in ca. 85% yields (Scheme 1). Fur-
ther palladium-mediated cross-coupling of 2a [Pd(dba)2
(2 mol%), (2-furyl)3P (4 mol%)] and of 2b [Pd(OAc)2 (2
mol%), SPhos9 (4 mol%), 21 °C, 24 h] with iodobenzene
provided the reference materials 3a and 3b (Table 1, en-
The benzoperylene derivatives 8 were condensed in the
same manner. Alternatively, 4-iodoaniline and 2-amino-
5-iodopyridine were condensed with the anhydrides 5 and
8, respectively, and further cross-coupled with 2a
[Pd(dba)2 (2 mol%), (furyl)3P10 (4 mol%), 20 °C, 24 h] to
form the dyads 6a, 6e and 9a (Scheme 3), however, the
yields were slightly lower (47%, 52%, and 29% yield, re-
spectively, over two steps) than for the condensation of
the corresponding anhydrides with amines (70%, 72%,
and 75%). The benzoxadiazole derivatives 6c, 6d, 7a, 9b,
and 10a were prepared in the same way by the condensa-
tion of the corresponding amines with the anhydrides 5 or
8. Finally, the zinc compound 2a was cross-coupled with
the bromoperylenedicarboxylic imide 11 to form 12
SYNTHESIS 2012, 44, 3465–3477
Advanced online publication: 31.10.2012
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
DOI: 10.1055/s-0032-1316785; Art ID: SS-2012-T0176-OP
© Georg Thieme Verlag Stuttgart · New York

3466
H. Langhals et al.
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Table 1 Conditions for the Formation of 3a–h, 4a,b
Entry
X
Y
Z
Conditions
Product
Yield (%)
1
2
3
4
5
6
7
8
9
–
S
–
2a, 3-iodoaniline, Pd(OAc)2, SPhos, THF
2b, 3-iodoaniline, Pd(OAc)2, SPhos, THF
2a, PhI, Pd(dba)2, (2-furyl)3P, THF
4a
4b
3a
3b
3c
3d
3e
3f
61
55
83
69
61
59
53
54
42
–
O
S
–
CH
CH
CH
CH
N
H
O
S
H
2b, Pd(OAc)2, SPhos, PhI, THF
NH2
NH2
NH2
NH2
TMS
2a, 4-iodoaniline, Pd(OAc)2, SPhos, THF
2b, 4-iodoaniline, Pd(OAc)2, SPhos, THF
2a, 5-iodopyridin-2-amine, Pd(OAc)2, SPhos, THF
2b, 5-iodopyridin-2-amine, Pd(OAc)2, SPhos, THF
O
S
N
O
S
CH
2a, (4-bromophenyl)trimethylsilane, Pd(dba)2,
3g
(furyl)3P, THF
10
CH
S
I
from 3g: ICl, CH2Cl2
3h
93
Y
N
N
O
O
O
N
O
O
N
O
i, 3
i, 4
R
N
O
O
O
R
X
5
6
N
Y
O
N
O
O
N
O
N
R
7
R
N
R
N
O
O
O
O
Y
N
N
O
O
ii, 3
O
N
X
O
O
O
N
R
O
O
O
N
R
O
9
ii, 4
R
N
8
O
N
O
N
Y
N
O
O
N
R
O
10
Scheme 2 Synthesis of 2,1,3-benzothiadiazoloperylenes (see Table 2). Reagents and conditions: (i) Zn(OAc)2, quinoline, 210 °C, 5 h; (ii)
Zn(OAc)2, microwaves.
Synthesis 2012, 44, 3465–3477
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Benzothiadiazoloperylenes and Benzoxadiazoloperylenes
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Table 2 Condensation of Perylene Anhydrides
Entry
Compound X
Y
R
Substrates
Conditions
Yield (%) Crystallinity
1
2
3
4
5
6
5a
5b
6a
6b
6c
6d
–
–
CH(C6H13)2
CH(C9H18)2
CH(C6H13)2
CH(C9H18)2
CH(C6H13)2
CH(C6H13)2
–
–
–
–
–
–
crystalline
crystalline
amorphous
amorphous
amorphous
–
–
a
CH
CH
CH
N
S
S
O
O
–
Pd(dba)2, (2-furyl)3P, THF 60
Zn(OAc)2, quinoline, 210 °C 74
Zn(OAc)2, quinoline, 210 °C 70
Zn(OAc)2, quinoline, 210 °C 72
3c + 5b
3d + 5a
3f + 5a
predominantly
amorphous
b
7
6e
N
S
CH(C6H13)2
–
Pd(dba)2, (2-furyl)3P, THF 68
predominantly
amorphous
8
7a
10a
8a
9a
9b
9c
–
O
O
–
CH(C6H13)2
CH(C6H13)2
CH(C6H13)2
CH(C6H13)2
CH(C6H13)2
CH(C6H13)2
CH(C6H13)2
4b + 5a
4b + 8a
Zn(OAc)2, quinoline, 210 °C 80
amorphous
crystalline
–
9
–
quinoline, microwaves
75
10
11
12
13
14
–
c
CH
CH
N
S
–
Pd(dba)2, (2-furyl)3P, THF 42
crystalline
amorphous
amorphous
amorphous
O
S
3d + 8a
3e + 8a
3f + 8a
quinoline, microwaves
quinoline, 210 °C
74
75
77
9d
N
O
quinoline, microwaves
a From 2-(1-hexylheptyl)-9-(4-iodophenyl)anthra[2,1,9-def:6,5,10-d′e′f′]diisoquinoline-1,3,8,10-tetraone with 2a.
b From 2-(1-hexylheptyl)-9-(5-iodopyridin-2-yl)anthra[2,1,9-def:6,5,10-d′e′f′]diisoquinoline-1,3,8,10-tetraone with 2a.
c From 6-(4-iodophenyl)-2,10-bis(1-hexylheptyl)-1H-pyrrolo[3′,4′:4,5]pyreno[2,1,10-def:7,8,9-d′e′f′]diisoquinoline-1,3,5,7,9,11(2H,6H,10H)-
hexone with 2a.
O
N
O
O
N
O
ZnCl
2a
·LiCl
·MgCl2
N
N
S
O
N
O
O
N
I
O
Pd(dba)2, (2-furyl)3P
THF, r.t.
X
O
O
X
N
N
5c X = CH
5d X = N
6a X = CH
6e X = N
S
O
N
O
O
N
O
O
ZnCl
2a
·LiCl
·MgCl2
N
I
N
N
N
S
O
O
N
N
Pd(dba)2, (2-furyl)3P
THF, r.t.
S
O
N
O
O
N
9a
8b
Scheme 3
© Georg Thieme Verlag Stuttgart · New York
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H. Langhals et al.
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(Scheme 4). The zinc organometallic derivative of 3 was FRET. The fluorescence quantum yield of 6a and 6b, re-
prepared from the iodo compound 3h by means of zinc spectively, are close to 100% both for the irradiation of
chloride and magnesium, however proved to be less reac- the perylene chromophore and for the 2,1,3-benzothiadia-
tive than 2a in the cross-coupling with 11; better results zole unit, indicating the domination of the Förster-type
were obtained with the iodo compound 13 to form 14 energy transfer11 (FRET) over alternative processes for
(Scheme 4). Finally, a benzothiadiazole was directly at- deactivation.
tached to perylenetetracarboxylic bisimide by the conden-
sation of 5 with 4,7-dibromo-2,1,3-benzothiadiazol-5-
amine to form the crystalline 15 (for the structure, see the
experimental section).
The most bathochromic absorption of 9a is found at short-
er wavelengths than for 6a; additional absorption bands
were found caused by the attached heterocycle such as in
6a (Figure 2). The fluorescence of the basic perylene
The UV/Vis spectra of the heterocyclically extended per- chromophore in 9a was efficiently quenched. This is in-
ylene derivatives are dominated by the strong, structured, terpreted in terms of a photo-induced electron transfer
bathochromic absorption of the perylenecarboxylic imide (PET) from the electron-rich 2,1,3-benzothiadiazole to
chromophores. The absorption of 6a compared with the the comparably electron-deficient, electronically excited
purely aliphatically substituted reference compound N,N′- benzoperylene chromophore; compare with the litera-
bis(1-hexylheptyl)-3,4:9,10-perylenebis(dicarboximide)
(S-13) exhibits an additional weaker absorption between
290 and 380 nm caused by the attached 2,1,3-benzothiadi-
azole; see Figure 1. Interestingly the additional absorption
matches the emission of the mercury line at 365 nm as a
very intense UV light source. The fluorescence of the at-
tached heterocycle in 6a is completely suppressed and
only the strong, bathochromic emission of the perylene
unit was found indicating an efficient energy transfer by
ture.12
Figure 2 Thick line: UV/Vis absorption spectrum of 9a (CHCl3);
thin line: UV/Vis absorption spectrum of 6-cyclohexyl-2,10-bis(1-
hexylheptyl)-1H-pyrrolo[3′,4′:4,5]pyreno[2,1,10-def:7,8,9-d′e′f′]di-
isoquinoline-1,3,5,7,9,11(2H,6H,10H)-hexone as a typical example
for benzoperylenehexacarboxylic trisimides.
The UV/Vis spectra of 12 are slightly bathochromically
shifted in the visible compared with standard perylene-
3,4-dicarboximides; the typical double maximum struc-
ture is preserved; see Figure 3. There is an additional ab-
sorption of the heterocyclic side chain at about 300 nm.
The fluorescence spectrum is broad, slightly structured
Figure 1 UV/Vis absorption and fluorescence spectra (CHCl3); thin
line: Standard perylene dye S-13; thick line, left: Absorption of 6a;
thick line, right: fluorescence spectra of 6a; the spectra of 6b are con-
gruent to those of 6a.
S
O
O
N
O
i, 2a
N
N
R
N
O
R
Br
11
12 (crystalline)
S
O
N
O
O
N
O
ii, 3h
N
N
R
R
I
13
14 (amorphous)
Scheme 4 Synthesis of 2,1,3-benzothiadiazoloperylenes. Reagents and conditions: (i) Pd(OAc)2, SPhos (4 mol%), THF, 20 °C, 24 h; (ii) 1. 3h,
LiCl, Mg, ZnCl2, THF; 2. 13, Pd(dba)2, (furyl)3P.
Synthesis 2012, 44, 3465–3477
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Benzothiadiazoloperylenes and Benzoxadiazoloperylenes
3469
Figure 3 UV/Vis absorption and fluorescence spectra (CHCl3); thin
line: 2-(1-Hexylheptyl)-1H-perylo[3,4-cd]pyridine-1,3(2H)-dione as
typical example for perylene-3,4-dicarboxylic imides; thick line, left:
Absorption of 12, dotted line: 14; thick line, right: Fluorescence spec-
tra of 12 (thick line) and 14 (dotted line).
Figure 5 XRD spectrum of 6b (MoKα)
DLS measurement of this phase indicates the formation of
nanoparticles with a particle size of 28 nm; (Figure 6). A
REM micrograph of the evaporated solution verifies such
a nano structure (Figure 7). Obviously, the prolongation
of the swallow-tail alkyl side chain diminishes the molec-
ular interactions so far that no amorphous macroscopic
aggregates are formed such as for 6a, but the continuation
of aggregation stops at nanometer dimensions. Compound
6e with the more polar pyridyl spacer seems to be slightly
more ordered. The disordering effect of 2,1,3-benzothia-
diazole seems to be more general because it was also
found for compounds 9, 10, 12, and 14, however, not as
pronounced as for 6 where no tendency for the formation
of ordered arrangements could be detected for 6a and 6b,
respectively; see Figure 8 and compare with Figure 4.
and extends to the near infrared (NIR). The fluorescence
is strong where a fluorescence quantum yield of 90% was
obtained in chloroform. The introduction of a phenyl
spacer in 14 causes a further slight bathochromic shift
both for the UV/Vis absorption and fluorescence where
the structuring of the spectra is similar to 12, however less
pronounced. The fluorescence quantum yield of 14 in-
creased by the introduction of the phenyl spacer to close
to 100%.
The bichromophoric 6a dissolved in dichloromethane and
precipitated with methanol is obtained as an amorphous,
voluminous red precipitate without any tendency for crys-
tallization and resembles precipitated aluminum hydrox-
ide, except for the red color. The XRD spectrum indicates
an amorphous structure up to microscopic dimensions
since no sharp reflexes were obtained (Figure 4). A pro-
longation of the side chain in 6b lowers the molecular in-
teractions further and preserves the amorphous structure;
see Figure 5. Precipitation with methanol forms a red liq-
uid phase with the impression of homogeneity being able
to pass standard D4 glass filters.
Figure 6 DLS measurement of 6b precipitated with methanol from
dichloromethane
In summary, 2,1,3-benzothiadiazole and 2,1,3-benzoxadi-
azole moieties could be efficiently attached to perylene-
and benzoperylenecarboxylic imides by using a palladi-
um-catalyzed cross-coupling with the new zincated 2,1,3-
benzothiadiazoles 2a and 2,1,3-benzoxadiazoles 2b. Such
dyads were obtained as amorphous macroscopic (6a) and
amorphous nanomaterials (6b), respectively. The per-
ylene derivatives 6 exhibit FRET-type energy transfer
with efficiencies close to 100% and the similar benzoper-
ylene derivatives 9 highly efficient photoinduced charge
separation by electron transfer (PET), respectively. The
Figure 4 XRD spectrum of 6a (MoKα)
© Georg Thieme Verlag Stuttgart · New York
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H. Langhals et al.
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d′e′f′]diisoquinolin-2(1H)-yl]ethyl}-1H-pyrrolo[3′,4′:4,5]pyreno[2,1,10-
def:7,8,9-d′e′f′]diisoquinoline-1,3,5,7,9,11(2H,6H,10H)-hexone
(C25)14 (RN 335458-21-4). 2-Dicyclohexyl(2′,6′-dimethoxybiphe-
nyl)phosphine = SPhos. For NMR assignments, Hbper and Hper are
used to indicate protons on the benzoperylene and perylene moi-
eties, respectively.
2,1,3-Benzothiadiazol-4-ylzinc Chloride (2a)
A 0.6 M soln of TMP2Mg·2LiCl in THF (23.0 mL) was added in a
dry Schlenk tube under an argon atmosphere dropwise to a soln of
2,1,3-benzothiadiazole (1a; 1.4 g, 10 mmol) in anhyd THF (10 mL)
at –40 °C. The mixture was stirred for 14 h at this temperature and
then treated dropwise with 1.0 M ZnCl2 in anhyd THF (15 mL) and
stirred at –40 °C for 30 min. The mixture was allowed to warm to
20 °C to give the zinc reagent 2a; yield: ca. 85%.
2,1,3-Benzoxadiazol-4-ylzinc Chloride (2b)
A 1.2 M soln of TMPMgCl·LiCl in anhyd THF (1.7 mL) was added
in a dry Schlenk tube under an argon atmosphere dropwise to a soln
of 2,1,3-benzoxadiazole (1b; 220 mg, 1.8 mmol) in anhyd THF
(2 mL) at –5 °C. The mixture was stirred for 14 h at this temperature
and then treated dropwise with 1.0 M ZnCl2 in anhyd THF (2.1 mL)
and stirred at –5 °C for 30 min. The mixture was allowed to warm
up to 20 °C to provide the zinc reagent 2b; yield: ca. 80%.
Figure 7 REM micrograph of 6b precipitated with methanol from di-
chloromethane and then evaporated
4-(2,1,3-Benzothiadiazol-4-yl)aniline (3c); Typical Procedure
Under argon, 0.25 M soln of 2a in anhyd THF (3 mmol), Pd(OAc)2
(14 mg, 0.06 mmol), SPhos (49 mg, 0.12 mmol), and 4-iodoaniline
(855 mg, 3.9 mmol) were stirred at 50 °C for 24 h. The reaction was
quenched by the addition of sat. aq NH4Cl soln (15 mL) and extract-
ed with CH2Cl2 (3 × 50 mL). The combined extracts were dried
(MgSO4), evaporated in vacuo, and purified by column chromatog-
raphy (silica gel, CH2Cl2) to give 3c as a brown solid; yield: 415 mg
(61%); mp 131.6–133.2 °C.
IR (ATR): 1627 (m), 1608 (m), 1512 (s), 1297 (m), 1181 (m), 1124
(m), 827 (m), 802 (s), 753 cm–1 (vs).
1H NMR (400 MHz, DMSO-d6): δ = 7.94–7.88 (m, 1 H), 7.76–7.67
(m, 4 H), 6.72–6.68 (m, 2 H), 5.40 (br s, 2 H).
13C NMR (100 MHz, DMSO-d6): δ = 155.3, 152.8, 149.2, 134.0,
Figure 8 XRD spectrum of 12 (MoKα)
130.3, 129.9, 125.4, 123.9, 118.3, 113.6.
MS (70 eV, EI): m/z (%) = 229 (5), 228 (15), 227 (100) [M+], 226
(15), 211 (5), 194 (5), 181 (4), 168 (3), 140 (4), 114 (5).
HRMS (EI): m/z [M]+ calcd for C12H9N3S: 227.0517; found:
227.0517.
combination of these photophysical effects and the amor-
phous structures make such materials especially interest-
ing for photovoltaic and OLED applications because they
avoid interfering grain boundaries of microcrystallinity.
One may expect that 2,1,3-benzothiadiazole and 2,1,3-
benzoxadiazole moieties are more generally useful for the
generation of amorphous structures when combined with
chromophores.
3-(2,1,3-Benzothiadiazol-4-yl)aniline (4a)
Following the typical procedure for 3c using 0.25 M 2a in anhyd
THF (3 mmol), Pd(OAc)2 (14 mg, 0.06 mmol), SPhos (49 mg,
0.12 mmol), 3-iodoaniline (855 mg, 3.9 mmol), and sat. aq NH4Cl
soln (15 mL) with purification by column chromatography (silica
gel, pentane–EtOAc, 3:1) gave 4a as an ochre solid; yield: 414 mg
(61%); mp 93.2–94.6 °C.
IR (ATR): 3435 (m), 3346 (m), 1623 (m), 1582 (m), 1478 (m), 1165
(m), 850 (m), 778 (s), 760 (s), 698 cm–1 (s).
1H NMR (400 MHz, DMSO-d6): δ = 8.03 (dd, J = 8.6, 1.4 Hz, 1 H),
7.78–7.71 (m, 2 H), 7.18–7.14 (m, 2 H), 7.05–7.03 (m, 1 H), 6.67–
6.64 (m, 1 H), 5.20 (br s, 2 H).
13C NMR (100 MHz, DMSO-d6): δ = 155.1, 152.8, 148.7, 137.5,
134.4, 130.1, 128.9, 127.5, 119.9, 116.8, 114.6, 114.0.
MS (70 eV, EI): m/z (%) = 229 (4), 228 (11), 227 (100) [M+], 226
(14), 211 (5), 200 (3), 199 (3), 194 (2), 181 (3), 140 (3), 114 (3).
HRMS (EI): m/z [M]+ calcd for C12H9N3S: 227.0517; found:
227.0503.
The reactions were carried out under an argon atmosphere in flame-
dried glassware if indicated. Syringes which were used to transfer
anhydrous solvents or reagents were purged with argon prior to use.
THF was continuously refluxed and freshly distilled from sodium
benzophenone ketyl under N2. Column chromatography was per-
formed using silica gel (0.040–0.063 mm, 230–400 mesh ASTM)
from Merck. IR spectra: Perkin Elmer 1420 Ratio Recording Infra-
red Spectrophotometer, FT 1000 and Perkin Elmer BXII FT-IR
with ATR-unit; UV/Vis spectra: Varian Cary 5000 and Bruins
Omega 20; fluorescence spectra: Varian Cary Eclispe; NMR spec-
troscopy: Varian Vnmrs 600 (600 MHz); mass spectroscopy: Finni-
gan MAT 95. References for the fluorescence quantum yield: A =
N,N′-Bis(1-hexylheptyl)-3,4:9,10-perylenebis(dicarboximide) (S-
13)13 (RN 110590-84-6); B = perylene-3,4,9,10-tetramethyl ester
(RN 53159-49-2); C = 2,10-bis(1-hexylheptyl)-6-{2-[3,8,9,10-
tetrahydro-9-(1-octylnonyl)-1,3,8,10-tetraoxoanthra[2,1,9-def:6,5,10-
5-(2,1,3-Benzothiadiazol-4-yl)pyridin-2-amine (3e)
Following the typical procedure for 3c using 0.25 M 2a in anhyd
THF (3 mmol), Pd(OAc)2 (14 mg, 0.06 mmol), SPhos (49 mg,
Synthesis 2012, 44, 3465–3477
© Georg Thieme Verlag Stuttgart · New York

PAPER
Benzothiadiazoloperylenes and Benzoxadiazoloperylenes
3471
0.12 mmol), 5-iodopyridin-2-amine (885 mg, 3.9 mmol), and sat.
aq NH4Cl soln (15 mL) with purification by column chromatogra-
phy (silica gel, EtOAc) gave 3e as a yellow solid; yield: 360 mg
(53%); mp 194.9–196.6 °C.
1178 (w), 1141 (w), 1016 (w), 892 (w), 871 (w), 836 (m), 815 (m),
797 (s), 754 cm–1 (vs).
1H NMR (400 MHz, DMSO-d6): δ = 7.82–7.79 (m, 3 H), 7.65–7.56
(m, 2 H), 6.72–6.69 (m, 2 H), 5.58 (br s, 2 H).
IR (ATR): 1640 (s), 1628 (s), 1594 (m), 1506 (m), 1482 (s), 1382
(m), 1272 (m), 827 (m), 805 (s), 755 cm–1 (vs).
1H NMR (400 MHz, DMSO-d6): δ = 8.60 (dd, J = 2.5, 0.7 Hz, 1 H),
8.03 (dd, J = 8.6, 2.5 Hz, 1 H), 7.98–7.93 (m, 1 H), 7.75–7.70 (m, 2
H), 6.59 (dd, J = 8.7, 0.7 Hz, 1 H), 6.25 (br s, 2 H).
13C NMR (100 MHz, DMSO-d6): δ = 159.6, 155.1, 152.6, 148.2,
137.4, 131.4, 130.3, 125.5, 120.7, 119.0, 107.5.
MS (70 eV, EI): m/z (%) = 229 (11), 228 (100) [M+], 227 (21), 201
(11), 200 (7), 69 (8), 57 (10), 55 (10), 43 (8), 41 (6).
HRMS (EI): m/z [M]+ calcd for C11H8N4S: 228.0470; found:
228.0461.
13C NMR (100 MHz, DMSO-d6): δ = 150.1, 149.7, 148.2, 133.2,
129.3, 129.1, 125.3, 121.6, 113.8, 112.1.
MS (70 eV, EI): m/z (%) = 212 (13), 211 (100) [M+], 210 (7), 194
(8), 182 (10), 181 (53), 179 (7), 155 (11), 154 (10), 153 (9), 127
(10).
HRMS (EI): m/z [M]+ calcd for C12H9N3O: 211.0746; found:
211.0741.
3-(2,1,3-Benzoxadiazol-4-yl)aniline (4b)
Following the typical procedure for 3d using 0.2 M 2b in anhyd
THF (1.4 mmol), Pd(OAc)2 (7 mg, 0.03 mmol), SPhos (25 mg,
0.06 mmol), and 3-iodoaniline (375 mg, 1.7 mmol) with purifica-
tion by column chromatography (silica gel, pentane–EtOAc, 2:1)
gave 4b as a yellow solid; yield 160 mg (55%); mp 95.8–97.4 °C.
4-[4-(Trimethylsilyl)phenyl]-2,1,3-benzothiadiazole (3g)
Following the typical procedure for 3c using 0.25 M 2a in anhyd
THF (3 mmol), Pd(dba)2 (25 mg, 0.06 mmol), (furyl)3P (mg,
0.12 mmol), (4-bromophenyl)trimethylsilane (1.03 g, 4.5 mmol),
and sat. aq NH4Cl soln (10 mL) with purification by column chro-
matography (silica gel, pentane) gave 3g as a light-yellow solid;
yield: 355 mg (42%); mp 120.6–122.4 °C.
IR (ATR): 3400 (w), 1602 (m), 1583 (m), 1311 (w), 1018 (w), 889
(w), 870 (m), 859 (m), 784 (s), 746 (vs), 694 cm–1 (s).
1H NMR (400 MHz, DMSO-d6): δ = 9.96 (dd, J = 8.8, 1.0 Hz, 1 H),
7.71–7.64 (m, 2 H), 7.23–7.16 (m, 2 H), 7.12–7.09 (m, 1 H), 6.70–
6.67 (m, 1 H), 5.30 (br s, 2 H).
IR (ATR): 3058 (w), 1946 (w), 1595 (w), 1474 (w), 1412 (w), 1168
(w), 850 (m), 825 (m), 799 (vs), 751 (s), 713 cm–1 (w).
1H NMR (300 MHz, CDCl3): δ = 8.01–7.97 (m, 1 H), 7.91–7.88 (m,
2 H), 7.71–7.66 (m, 4 H), 0.32 (s, 9 H).
13C NMR (75 MHz, CDCl3): δ = 155.6, 153.6, 140.9, 137.7, 134.7,
133.6, 129.6, 128.5, 127.7, 120.6, –1.1.
MS (70 eV, EI): m/z (%) = 286 (3), 285 (5), 284 (22) [M+], 272 (2),
271 (9), 270 (19), 269 (100), 253 (2), 239 (6), 135 (4).
HRMS (EI): m/z [M]+ calcd for C15H16N2SSi: 284.0803; found:
13C NMR (100 MHz, DMSO-d6): δ = 149.6, 149.1, 148.2, 135.4,
133.0, 129.7, 129.4, 128.5, 115.6, 114.8, 114.4, 113.4.
MS (70 eV, EI): m/z (%) = 212 (10), 211 (76) [M+], 182 (16), 181
(100), 179 (9), 168 (11), 154 (17), 153 (8), 149 (8), 127 (12).
HRMS (EI): m/z [M]+ calcd for C12H9N3O: 211.0746; found:
211.0737.
5-(2,1,3-Benzoxadiazol-4-yl)pyridin-2-amine (3f)
Following the typical procedure for 3d using 0.25 M 2b in anhyd
THF (1.4 mmol), Pd(OAc)2 (7 mg, 0.03 mmol), SPhos (25 mg,
0.06 mmol), and 5-iodopyridin-2-amine (375 mg, 1.7 mmol) with
purification by column chromatography (silica gel, EtOAc) gave 3f
as an orange solid; yield: 160 mg (54%); mp 166.9–168.8 °C.
284.0799.
4-(4-Iodophenyl)-2,1,3-benzothiadiazole (3h)
ICl (2 mL) was added to thiadiazole 3g (284 mg, 1 mmol) in
CH2Cl2 (2 mL) and the mixture was stirred at 0 °C for 3 h. The re-
action was quenched by the addition of sat. aq Na2S2O3 soln
(10 mL) and extracted with CH2Cl2 (3 × 30 mL). The combined ex-
tracts were dried (MgSO4), evaporated in vacuo, and purified by
column chromatography (silica gel, pentane–Et2O, 200:1) to give
3h as a light-yellow solid; yield: 316 mg (93%); mp 71.2–72.9 °C.
IR (ATR): 3414 (m), 3322 (w), 3118 (m), 1653 (s), 1612 (m), 1600
(s), 1545 (w), 1505 (vs), 1395 (s), 1372 (m), 1334 (w), 1322 (m),
1298 (m), 1269 (m), 1139 (m), 1081 (w), 1011 (w), 889 (w), 872
(w), 815 (w), 797 (m), 759 (w), 744 (s), 713 (w), 661 cm–1 (w).
1H NMR (400 MHz, DMSO-d6): δ = 8.69–8.68 (m, 2 H), 8.06 (dd,
J = 8.7, 2.6 Hz, 1 H), 7.87 (dd, J = 8.9, 0.7 Hz, 1 H), 7.71 (dd,
J = 6.9, 0.8 Hz, 1 H), 7.62 (dd, J = 8.9, 6.9 Hz, 1 H), 6.60 (dd,
J = 8.7, 0.7 Hz, 1 H), 6.41 (br s, 2 H).
IR (ATR): 3063 (w), 1594 (w), 1249 (m), 1130 (w), 1096 (w), 895
(w), 840 (s), 823 (s), 803 (s), 756 (vs), 678 cm–1 (m).
1H NMR (300 MHz, CDCl3): δ = 8.06–8.00 (m, 1 H), 7.90–7.85 (m,
13C NMR (100 MHz, DMSO-d6): δ = 160.1, 149.6, 148.0, 147.9,
2 H), 7.72–7.67 (m, 4 H).
136.3, 133.2, 126.8, 125.9, 118.6, 113.0, 107.9.
13C NMR (75 MHz, CDCl3): δ = 155.6, 153.2, 137.8, 136.8, 133.4,
MS (70 eV, EI): m/z (%) = 213 (15), 212 (100) [M+], 196 (9), 185
131.0, 129.6, 127.6, 121.0, 94.5.
(8), 182 (11), 155 (17), 142 (8), 128 (8), 57 (8).
MS (70 eV, EI): m/z (%) = 339 (15), 338 (100), 212 (10), 211 (57),
HRMS (EI): m/z [M]+ calcd for C11H8N4O: 212.0698; found:
178 (15), 165 (7), 152 (9), 140 (12), 58 (11), 43 (39).
212.0690.
HRMS (EI): m/z [M]+ calcd for C12H7IN2S: 337.9375; found:
337.9370.
4-Phenyl-2,1,3-benzoxadiazole (3b)
A 0.25 M soln of 2b in anhyd THF (1.4 mmol) under argon,
Pd(OAc)2 (7 mg, 0.03 mmol), (furyl)3P (25 mg, 0.06 mmol), and
iodobenzene (347 mg, 1.7 mmol) were stirred at 25 °C for 6 h. The
reaction was quenched with sat. aq NH4Cl soln (10 mL) and extract-
ed with CH2Cl2 (3 × 30 mL). The combined extracts were dried
(MgSO4), evaporated in vacuo, and purified by column chromatog-
raphy (silica gel, pentane) to give 3b as a light-brownish solid;
yield: 244 mg (69%); mp 64.5–65.3 °C; Rf = 0.8 (toluene).
4-(2,1,3-Benzoxadiazol-4-yl)aniline (3d); Typical Procedure
Under argon, 0.25 M 2b in anhyd THF (1.4 mmol), Pd(OAc)2
(7 mg, 0.03 mmol), SPhos (25 mg, 0.06 mmol), and 4-iodoaniline
(375 mg, 1.7 mmol) were stirred at 50 °C for 24 h. The reaction was
quenched by the addition of sat. aq NH4Cl soln (10 mL) and extract-
ed with CH2Cl2 (3 × 30 mL). The combined extracts were dried
(MgSO4), evaporated in vacuo, and purified by column chromatog-
raphy (silica gel, pentane–EtOAc, 4:1) to give 3d as a brown solid;
yield: 175 mg (59%); mp 115.4–116.6 °C.
IR (ATR): 3082 (w), 1582 (s), 1494 (m), 1016 (m), 828 (m), 803
(m), 761 (s), 750 (s), 697 (s), 679 cm–1 (m).
IR (ATR): 3453 (w), 3364 (m), 3217 (w), 1626 (m), 1603 (s), 1544
(w), 1510 (s), 1447 (w), 1423 (w), 1373 (w), 1302 (m), 1276 (m),
1H NMR (600 MHz, CDCl3, 27.0 °C, TMS): δ = 7.99–7.97 (m, 2 H,
HPh), 7.79 (dd, 3JH,H = 8.9 Hz, 4JH,H = 0.8 Hz, 1 H, Harom), 7.57 (dd,
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 3465–3477

3472
H. Langhals et al.
PAPER
3JH,H = 6.8 Hz, 4JH,H = 0.8 Hz, 1 H, Harom), 7.54–7.51 (m, 2 H, HPh),
7.49 (dd, 3JH,H = 6.8 Hz, 3JH,H = 8.9 Hz, 1 H, Harom), 7.47–7.44 (m,
1 H, HPh).
13C NMR (150 MHz, CDCl3, 27.0 °C): δ = 149.8, 148.6, 135.3,
131.8, 130.5, 129.3, 128.9, 128.4, 128.0, 115.0.
MS (70 eV, EI): m/z (%) = 196 (88) [M+], 166 (100) [M+ – NO].
HRMS: m/z [M]+ calcd for C12H8N2O: 196.0637; found: 196.0631.
IR (ATR): 3476 (w), 2926 (m), 1696 (s), 1660 (s), 1594 (s),
1352 (s), 1254 (s), 864 (m), 810 (s), 793 (m), 746 cm–1 (m).
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 8.74–8.64 (m, 8 H,
3
3
Hper), 8.18 (d, JH,H = 8.3 Hz, 2 H, Harom), 8.05 (d, JH,H = 8.8 Hz,
3
1 H, Harom), 7.81 (d, JH,H = 7.1 Hz, 1 H, Harom), 7.73 (dd,
3
3
3JH,H = 7.2 Hz, JH,H = 8.5 Hz, 1 H, Harom), 7.53 (d, JH,H = 8.2 Hz,
2 H, Harom), 5.23–5.16 (m, 1 H, CH), 2.29–2.23 (m, 2 H, β-CH2),
1.92–1.83 (m, 2 H, β-CH2), 1.39–1.19 (m, 16 H, 8 CH2), 0.83 (t,
3JH,H = 7.0 Hz, 6 H, 2 CH3).
Anal. Calcd for C12H8N2O (196.1): C, 73.46; H, 4.11; N, 14.28.
Found: C, 73.35; H, 4.12; N, 14.04.
13C NMR (150 MHz, CDCl3, 27 °C): δ = 163.6, 155.6, 153.4,
137.9, 135.3, 135.1, 134.4, 133.6, 132.0, 130.3, 129.6, 128.8, 128.1,
126.8, 126.5, 123.4, 123.3, 123.1, 121.0, 54.8, 32.4, 31.8, 29.7,
29.2, 26.9, 22.6, 14.0.
8-(2,1,3-Benzothiadiazol-4-yl)-2-(1-hexylheptyl)-1H-perylo[3,4-
cd]pyridine-1,3(2H)-dione (12)
Under an argon atmosphere, 0.3 M 2a in anhyd THF (0.85 mmol),
Pd(OAc)2 (5 mg, 0.02 mmol), SPhos (16 mg, 0.04 mmol), and 8-
bromo-2-(1-hexylheptyl)-1H-perylo[3,4-cd]pyridine-1,3(2H)-di-
one (11; 63 mg, 0.13 mmol) were stirred at 20 °C for 24 h. The re-
action was quenched by the addition of sat. aq NH4Cl soln (5 mL)
and extracted with CH2Cl2 (3 × 30 mL). The combined extracts
were dried (MgSO4), evaporated in vacuo, dissolved in a small
amount of CH2Cl2, and purified by column chromatography (silica
gel, CH2Cl2, fraction with bright red color). The product dissolved
in CH2Cl2 was precipitated with MeOH and collected by vacuum
filtration to give 12 as a red solid; yield: 39 mg (47%); mp 184.4–
184.7 °C; Rf = 0.56 (CH2Cl2).
MS (DEP/EI): m/z (%) = 783 (36) [M+ + H], 600 (100) [M+
C13H26].
HRMS: m/z [M]+ calcd for C49H42N4O4S: 782.2927; found:
782.2845.
–
UV/Vis (CHCl3): λmax (ε)= 315.9 (17400), 352.0 (10500), 459.1
(19100), 491.0 (52700), 527.4 nm (87900).
Fluorescence (CHCl3): λmax (Irel) = 534.2 (1.00), 576.8 (0.51),
625.1 nm (0.12).
Fluorescence
quantum
yield
(CHCl3,
λexc = 491 nm,
E
491 nm, 1 cm = 0.1303, reference: A with Φ = 1.00): 1.00.
IR (ATR): 3050 (w), 2924 (s), 1688 (s), 1650 (s), 1592 (s),
1456 (m), 1352 (s), 854 (m), 808 (s), 752 cm–1 (s).
Fluorescence quantum yield (CHCl3, λexc = 353 nm, E353 nm, 1 cm
0.0026, reference: C with Φ = 1.00): 1.00.
=
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 8.59–8.47 (m, 3 H,
Anal. Calcd for C49H42N4O4S (782.3): C, 75.17; H, 5.41; N, 7.16; S,
4.10. Found: C, 75.27; H, 5.48; N, 6.81; S, 4.02.
H
per), 8.39 (m, 3 H, Harom), 8.17 (dd, 3JH,H = 8.7 Hz, 4JH,H = 1.2 Hz,
1 H, Harom), 7.84–7.80 (m, 1 H, Harom), 7.77–7.72 (m, 2 H, Harom),
7.63 (d, 3JH,H = 8.4 Hz, 1 H, Harom), 7.47 (m, 1 H, Harom), 5.24–5.17
(m, 1 H, CH), 2.31–2.22 (m, 2 H, β-CH2), 1.91–1.83 (m, 2 H, β-
2-[4-(2,1,3-Benzothiadiazol-4-yl)pyridin-2-yl]-9-(1-hexylhep-
tyl)anthra[2,1,9-def:6,5,10-d′e′f′]diisoquinoline-1,3,8,10-tetra-
one (6e)
Following the typical procedure for 6a using 0.3 M 2a in anhyd
THF (0.85 mmol), Pd(dba)2 (12 mg, 0.02 mmol), (2-furyl)3P (9 mg,
3
CH2), 1.40–1.20 (m, 16 H, 8 CH2), 0.83 (t, JH,H = 7.0 Hz, 6 H, 2
CH3).
13C NMR (150 MHz, CDCl3, 27 °C): δ = 165.1, 164.1, 155.1,
154.3, 138.1, 136.8, 136.5, 133.2, 132.8, 132.0, 131.1, 130.3, 129.8,
129.7, 129.5, 129.4, 129.1, 128.8, 128.3, 127.0, 126.5, 123.7, 123.0,
121.6, 120.4, 120.3, 54.4, 32.4, 31.8, 29.3, 27.0, 22.6, 14.1.
MS (DEP/EI): m/z (%) = 637 (42) [M+], 455 (100) [M+ – C13H26].
HRMS: m/z [M]+ calcd for C41H39N3O2S: 637.2763; found:
0.04 mmol)
and
2-(1-hexylheptyl)-9-(5-iodopyridin-2-yl)an-
thra[2,1,9-def:6,5,10-d′e′f′]diisoquinoline-1,3,8,10-tetraone13
(150 mg, 191 μmol) and sat. aq NH4Cl soln (5 mL) with and purifi-
cation by column chromatography (fine silica gel, CH2Cl2–MeOH,
60:1, 1st main fraction with bright-red color). The product dissolved
in a small amount of CH2Cl2 was precipitated with MeOH, collected
by vacuum filtration, and dried in vacuo to give 6e as a predomi-
nantly amorphous red material; yield: 103 mg (68%); mp > 300 °C;
Rf = 0.45 (CH2Cl2–MeOH, 60:1).
637.2751.
UV/Vis (CHCl3): λmax (ε) = 314.0 (15600), 489.5 (37500),
513.3 nm (38400).
IR (ATR): 3342 (w), 3067 (w), 2922 (m), 1696 (s), 1654 (s),
1592 (s), 1576 (s), 1338 (s), 1252 (s), 810 (s), 745 cm–1 (s).
Fluorescence (CHCl3): λmax = 557.3 nm.
Fluorescence
quantum
yield
(CHCl3,
λexc = 491 nm,
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 9.26 (s, 1 H, Harom),
E491 nm, 1 cm = 0.0195, reference: A with Φ = 1.00): 0.90.
8.70–8.57 (m, 9 H, Hper, Harom), 8.10 (d, 3JH,H = 8.8 Hz, 1 H, Harom),
3
3
Anal. Calcd for C41H39N3O2S (637.3): C, 77.21; H, 6.16; N, 6.59; S,
5.03. Found: C, 76.84; H, 6.30; N, 6.49; S, 5.12.
7.86 (d, JH,H = 6.8 Hz, 1 H, Harom), 7.77 (dd, JH,H = 8.8 Hz,
3JH,H = 6.9 Hz, 1 H, Harom), 7.64 (d, JH,H = 8.1 Hz, 1 H, Harom),
3
5.22–5.17 (m, 1 H, CH), 2.29–2.22 (m, 2 H, β-CH2), 1.92–1.86 (m,
2 H, β-CH2), 1.38–1.20 (m, 16 H, 8 CH2), 0.83 (t, JH,H = 7.1 Hz,
6 H, 2 CH3).
13C NMR (150 MHz, CDCl3, 27 °C): δ = 164.5, 163.4, 155.2,
153.1, 149.8, 148.8, 139.3, 135.2, 134.1, 133.6, 131.7, 130.1, 129.8,
129.5, 128.3, 126.6, 126.3, 123.8, 123.1, 123.0, 121.9, 54.8, 32.4,
31.7, 29.2, 27.0, 22.6, 14.0.
3
2-[4-(2,1,3-Benzothiadiazol-4-yl)phenyl]-9-(1-hexylheptyl)an-
thra[2,1,9-def:6,5,10-d′e′f′]diisoquinoline-1,3,8,10-tetraone
(6a); Typical Procedure
Under an argon atmosphere, 0.3 M 2a in anhyd THF (0.85 mmol),
Pd(dba)2 (12 mg, 0.02 mmol), (2-furyl)3P (9 mg, 0.04 mmol), and
2-(1-hexylheptyl)-9-(4-iodophenyl)anthra[2,1,9-def:6,5,10-d′e′f′]di-
isoquinoline-1,3,8,10-tetraone13 (100 mg, 129 μmol) were stirred at
21 °C for 24 h. The reaction was quenched by the addition of sat. aq
NH4Cl soln (5 mL) and extracted with CH2Cl2 (3 × 30 mL), dried
(MgSO4), evaporated in vacuo, dissolved in a small amount of
CH2Cl2, and purified by column chromatography (silica gel,
CH2Cl2, fraction with bright-red color). The product dissolved in
CH2Cl2 was precipitated with MeOH and collected by vacuum fil-
tration to give 6a as an amorphous red material; yield: 47 mg
(60%); mp >300 °C; Rf = 0.1 (silica gel, CH2Cl2).
MS (DEP/EI): m/z (%) = 784 (22) [M+ + H], 601 (100) [M+
–
C13H26].
HRMS: m/z [M]+ calcd for C48H41N5O4S: 783.2879; found:
783.2876.
UV/Vis (CHCl3): λmax (ε)= 315.0 (15400), 349.3 (8600), 459.6
(19800), 491.0 (54800), 527.4 nm (91400).
Fluorescence (CHCl3): λmax (Irel) = 534.2 (1.00), 577.1 (0.51),
625.7 nm (0.12).
Synthesis 2012, 44, 3465–3477
© Georg Thieme Verlag Stuttgart · New York

PAPER
Benzothiadiazoloperylenes and Benzoxadiazoloperylenes
3473
Fluorescence
quantum
yield
(CHCl3,
λexc = 491 nm,
1.84 (m, 2 H, β-CH2), 1.40–1.18 (m, 16 H, 8 CH2), 0.84 (t,
3JH,H = 6.8 Hz, 6 H, 2 CH3).
E491 nm, 1 cm = 0.0135, reference: A with Φ = 1.00): 1.00.
Fluorescence quantum yield (CHCl3, λexc = 353 nm, E353 nm, 1 cm
0.0027, reference: C with Φ = 1.00): 0.98.
=
13C NMR (150 MHz, CDCl3, 27.0 °C): δ = 163.5, 149.8, 148.4,
135.9, 135.7, 135.3, 131.9, 129.9, 129.4, 129.3, 129.1, 128.5, 126.7,
126.6, 123.1, 116.7, 115.5, 54.6, 32.3, 32.2, 31.6, 29.6, 29.2, 28.9,
26.9, 26.7, 26.6, 22.4, 13.9.
MS (DEP/EI): m/z (%) = 766 (37) [M+], 584 (100) [M+ – C13H26].
HRMS: m/z [M]+ calcd for C49H42N4O5: 766.3157; found:
Anal. Calcd for C48H41N5O4S (783.3): C, 73.54; H, 5.27; N, 8.93; S,
4.09; found: C, 73.33; H, 5.34; N, 8.90; S, 4.16.
6-[4-(2,1,3-Benzothiadiazol-4-yl)phenyl]-2,10-bis(1-hexylhep-
tyl)-1H-pyrrolo[3′,4′:4,5]pyreno[2,1,10-def:7,8,9-d′e′f′]diiso-
quinoline-1,3,5,7,9,11(2H,6H,10H)-hexone (9a)
766.3155.
Following the typical procedure for 6a using 0.3 M 2a in anhyd
THF (0.85 mmol), Pd(dba)2 (12 mg, 0.02 mmol), (2-furyl)3P (9 mg,
0.04 mmol), and 6-(4-iodophenyl)-2,10-bis(1-hexylheptyl)-1H-
pyrrolo[3′,4′:4,5]pyreno[2,1,10-def:7,8,9-d′e′f′]diisoquinoline-
1,3,5,7,9,11(2H,6H,10H)-hexone (210 mg, 198 μmol), and sat. aq
NH4Cl soln (5 mL) to give 9a as a yellow solid; yield: 88 mg (42%);
mp > 300 °C; Rf = 0.21 (CHCl3).
UV/Vis (CHCl3): λmax (ε) = 345.5 (12600), 459.8 (19600), 491.0
(53600), 527.4 nm (89300).
Fluorescence (CHCl3): λmax (Irel) = 534.8 (1.00), 577.2 nm (0.51).
Fluorescence quantum yield (CHCl3, λexc = 490 nm, E490 nm, 1 cm
0.0122, reference A with Φ = 1.00): 0.93.
=
=
Fluorescence quantum yield (CHCl3, λexc = 350 nm, E350 nm, 1 cm
0.0032, reference: C with Φ = 1.00): 0.85.
IR (ATR): 3074 (w), 2924 (s), 1710 (s), 1661 (s), 1364 (s),
1316 (s), 846 (m), 811 (s), 764 (s), 749 cm–1 (s).
Anal. Calcd for C49H42N4O5 (766:3): C, 76.74; H, 5.52; N, 7.31.
Found: C, 76.33; H, 5.69; N, 7.21.
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 10.34–10.30 (m,
2 H, Hbper), 9.18–9.06 (m, 4 H, Hbper), 8.26 (d, 3JH,H = 8.4 Hz, 2 H,
arom), 8.06 (dd, 3JH,H = 8.8 Hz, 4JH,H = 1.0 Hz, 1 H, Harom), 7.97 (d,
2-[5-(2,1,3-Benzoxadiazol-4-yl)pyridin-2-yl]-9-(1-hexylhep-
tyl)anthra[2,1,9-def:6,5,10-d′e′f′]diisoquinoline-
1,3,8,10(2H,9H)-tetraone (6d)
Following the typical procedure for 6c using 5-(2,1,3-benzoxadia-
zol-4-yl)pyridin-2-amine (3f; 43 mg, 0.20 mmol), 5a (115 mg,
200 μmol), Zn(OAc)2 (7.4 mg, 40 μmol), and quinoline (2.5 mL) to
give 6d as a predominantly amorphous red material; yield: 110 mg
(72%); mp >300 °C; Rf = 0.5 (CH2Cl2–MeOH, 60:1).
H
3JH,H = 8.2 Hz, 2 H, Harom), 7.87 (d, 3JH,H = 7.6 Hz, 1 H, Harom), 7.76
(dd, JH,H = 6.8 Hz, 3JH,H = 8.8 Hz, 1 H, Harom), 5.32–5.27 (m, 2 H,
3
CH), 2.42–2.32 (m, 4 H, β-CH2), 2.04–1.97 (m, 4 H, β-CH2), 1.48–
1.24 (m, 32 H, 8 CH2), 0.83 (t, 3JH,H = 7.1 Hz, 12 H, 2 CH3).
13C NMR (150 MHz, CDCl3, 27 °C, TMS): δ = 166.7, 164.4, 163.8,
163.3, 162.7, 155.6, 153.7, 137.2, 133.6, 131.4, 130.7, 130.1, 129.7,
128.9, 128.1, 127.4, 126.8, 126.7, 125.7, 125.0, 124.4, 123.7, 122.8,
121.0, 55.4, 32.4, 31.8, 29.3, 27.1, 22.6, 14.1.
IR (ATR): 3091 (w), 2924 (m), 1697 (s), 1653 (s), 1577 (s), 1339
(s), 1253 (s), 848 (m), 797 (s), 742 cm–1 (s).
MS (DEP/EI): m/z (%) = 1058 (9) [M+ + H], 876 (37) [M+ + H –
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 9.29 (d,
4JH,H = 2.5 Hz, 1 H, Harom), 8.75–8.64 (m, 9 H, Hper, Harom), 7.94 (dd,
3JH,H = 9.0 Hz, 4JH,H = 0.6 Hz, 1 H, Harom), 7.76 (dd, 3JH,H = 6.7 Hz,
4JH,H = 0.6 Hz, 1 H, Harom), 7.64 (dd, 3JH,H = 8.2 Hz, 4JH,H = 0.6 Hz,
C13H26], 694 (100) [M+ + H –2 C13H26].
HRMS: m/z [M]+ calcd for C66H67N5O6S: 1057.4812; found:
1057.4824.
3
3
1 H, Harom), 7.60 (dd, JH,H = 6.7 Hz, JH,H = 9.0 Hz, 1 H, Harom),
5.21–5.16 (m, 1 H, CH), 2.28–2.21 (m, 2 H, β-CH2), 1.90–1.84 (m,
2 H, β-CH2), 1.38–1.18 (m, 16 H, 8 CH2), 0.82 (t, 3JH,H = 7.0 Hz, 6
H, 2 CH3).
UV/Vis (CHCl3): λmax (ε) = 270.4 (44100), 315.9 (33600), 378.8
(38000), 409.4 (20600), 436.8 (39300), 466.8 nm (59400).
Fluorescence quantum yield (CHCl3, λexc = 436 nm,
E436 nm, 1 cm = 0.0140, reference: A with Φ = 1.00): <0.01.
13C NMR (150 MHz, CDCl3, 27.0 °C): δ = 163.4, 149.7, 149.6,
148.8, 148.2, 138.6, 135.4, 134.2, 131.9, 131.6, 130.0, 129.5, 129.1,
126.7, 126.4, 126.3, 124.3, 123.4, 123.1, 123.0, 116.7, 54.8, 32.4,
31.7, 29.2, 26.9, 22.6, 14.0.
MS (DEP/EI): m/z (%) = 767 (14) [M+], 585 (100) [M+ – C13H26].
HRMS: m/z [M]+ calcd for C48H41N5O5: 767.3108; found:
Anal. Calcd for C66H67N5O6S (1057.5): C, 74.90; H, 6.38; N, 6.62;
S, 3.03; found: C, 74.56; H, 6.26; N, 6.62; S, 3.14.
2-[4-(2,1,3-Benzoxadiazol-4-yl)phenyl]-9-(1-hexylheptyl)an-
thra[2,1,9-def:6,5,10-d′e′f′]diisoquinoline-1,3,8,10(2H,9H)-tet-
raone (6c); Typical Procedure
Under argon, 4-(2,1,3-benzoxadiazol-4-yl)aniline (3d; 42 mg,
0.20 mmol), tetraone 5a (115 mg, 200 μmol), Zn(OAc)2 (7.4 mg,
40 μmol), and quinoline (2.5 mL) were stirred at 210 °C for 5 h
(deeply red mixture). The mixture was allowed to cool slightly, add-
ed dropwise with intense stirring to 2 M aq HCl (300 mL), stirred
for 2 h, and allowed to stand for 16 h. The product was collected by
vacuum filtration, washed with 2 M aq HCl (300 mL), hot distilled
H2O (300 mL), and a mixture of MeOH and distilled H2O (300 mL,
1:1), and dried in vacuo at 90 °C for 2 d. The residue was dissolved
in the minimal amount of CH2Cl2 and purified by column chroma-
tography (short column with alumina, CH2Cl2 and a further column
with silica gel, CH2Cl2, deeply red first fraction) to give 6c as an
amorphous red material; yield: 108 mg (70%); mp >300 °C; Rf = 0.2
(CH2Cl2).
767.3114.
UV/Vis (CHCl3): λmax (ε) = 334.4 (12000), 459.8 (19500), 491.0
(53400), 528.1 nm (88900).
Fluorescence (CHCl3) : λmax (Irel) = 534.7 (1.00), 577.2 nm (0.51).
Fluorescence quantum yield (CHCl3, λexc = 490 nm, E490 nm, 1 cm
0.0140, reference A with Φ = 1.00): 0.98.
=
Fluorescence quantum yield (CHCl3, λexc = 350 nm, E350 nm, 1 cm
0.0026, reference: C with Φ = 1.00): 1.00.
=
Anal. Calcd for C48H41N5O5 (767.3): C, 75.08; H, 5.38; N, 9.12.
Found: C, 74.91; H, 5.36; N, 9.07.
2-[3-(2,1,3-Benzoxadiazol-4-yl)phenyl)-9-(1-hexylheptyl)an-
thra[2,1,9-def:6,5,10-d′e′f′]diisoquinoline-1,3,8,10(2H,9H)-
tetraone (7a)
IR (ATR): 2925 (m), 1694 (s), 1658 (s), 1593 (s), 1345 (s), 1252 (s),
1176 (s), 843 (m), 810 (s), 744 cm–1 (s).
Following the typical procedure for 6c using 4b (44 mg,
0.21 mmol), 5a (115 mg, 200 μmol), Zn(OAc)2 (7.4 mg, 40 μmol),
and quinoline (2.5 mL) to give 7a as a red solid; yield: 122 mg
(80%); mp 287–289 °C; Rf = 0.4 (CH2Cl2).
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 8.80–8.68 (m, 8 H,
Hper ), 8.24 (d, JH,H = 8.8 Hz, 2 H, Harom), 7.87 (d, JH,H = 8.8 Hz,
1 H, Harom), 7.69 (d, 3JH,H = 6.8 Hz, 1 H, Harom), 7.59–7.53 (m, 3 H,
Harom), 5.23–5.17 (m, 1 H, CH), 2.30–2.22 (m, 2 H, β-CH2), 1.92–
3
3
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 3465–3477

3474
H. Langhals et al.
PAPER
IR (ATR): 2925 (m), 1701 (s), 1661 (s), 1595 (m), 1343 (s), 1174
(m), 851 (m), 809 (s), 784 (s), 744 cm–1 (s).
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 8.76–8.63 (m, 8 H,
6-[3-(2,1,3-Benzoxadiazol-4-yl)phenyl]-2,10-bis(1-hexylheptyl)-
1H-pyrrolo[3′4′:4,5]pyreno[2,1,10-def:7,8,9-d′e′f′]diisoquino-
line-1,3,5,7,9,11(2H,6H,10H)-hexone (10a); Typical Procedure
Aniline 4b (35 mg, 0.17 mmol), N,N′-bis(1-hexylheptyl)ben-
zo[ghi]perylene-2,3,8,9,11,12-hexacarboxylic-2,3:8,9-bis(dicar-
boximide)-11,12-anhydride (8a; 103 mg, 121 μmol), and quinoline
(2.0 mL) were stirred under argon and microwave radiation (180
W) at 210 °C for 5 h (dark yellow mixture). The mixture was al-
lowed to cool, added dropwise with intense stirring to 2 M aq HCl
(300 mL), stirred for 2 h, and allowed to stand for 16 h. The product
was collected by vacuum filtration, washed with 2 M aq HCl
(300 mL), hot distilled H2O (300 mL) and MeOH–H2O (1:1,
300 mL), and dried at 110 °C in vacuo for 2 d. The residue was dis-
solved in the minimal amount of CH2Cl2 and purified by column
chromatography (short column with alumina, CH2Cl2 and a further
column with silica gel, CH2Cl2, brightly yellow first fraction) to
give 10a as a yellow solid; yield: 94 mg (75%); mp >300 °C; Rf =
0.9 (CHCl3).
3
4
Hper), 8.20 (d, JH,H = 8.0 Hz, 1 H, Harom), 8.08 (dd, JH,H = 1.9 Hz,
4JH,H = 1.9 Hz, 1 H, Harom), 7.82 (d, 3JH,H = 9.0 Hz, 1 H, Harom), 7.75
3
3
(dd, JH,H = 7.9 Hz, JH,H = 7.9 Hz, 1 H, Harom), 7.69 (d,
3JH,H = 6.9 Hz, 1 H, Harom), 7.51–7.47 (m, 2 H, Harom), 5.22–5.16 (m,
1 H, CH), 2.29–2.22 (m, 2 H, β-CH2), 1.92–1.85 (m, 2 H, β-CH2),
1.39–1.19 (m, 16 H, 8 CH2), 0.83 (t, 3JH,H = 6.9 Hz, 6 H, 2 CH3).
13C NMR (150 MHz, CDCl3, 27 °C): δ = 163.5, 149.8, 148.4, 136.5,
135.8, 135.3, 134.2, 131.9, 131.7, 130.0, 129.8, 129.5, 129.3, 128.7,
128.7, 128.4, 126.7, 126.4, 123.4, 123.2, 123.1, 115.6, 54.8, 32.4,
31.8, 29.2, 26.9, 22.6, 14.0.
MS (DEP/EI): m/z (%) = 766 (37) [M+], 584 (100) [M+ – C13H26].
HRMS: m/z [M]+ calcd for C49H42N4O5: 766.3157; found:
766.3160.
UV/Vis (CHCl3): λmax (ε) = 338.1 (11800), 459.8 (18900), 491.0
(51500), 527.4 nm (85900).
IR (ATR): 2926 (m), 1710 (s), 1662 (s), 1366 (s), 1318 (s), 812 (m),
764 (m), 748 cm–1 (m).
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 10.34–10.18 (m,
2 H, Hbper), 9.16–9.02 (m, 4 H, Hbper), 8.48 (s, 1 H, Harom), 8.28 (m,
1 H, Harom), 7.95–7.91 (m, 1 H, Harom), 7.88–7.85 (m, 2 H, Harom),
7.82 (dd, JH,H = 7.9 Hz, JH,H = 7.9 Hz, 1 H, Harom), 7.58 (dd,
3JH,H = 6.9 Hz, 3JH,H = 8.8 Hz, 1 H, Harom), 5.34–5.26 (m, 2 H, CH),
2.40–2.32, (m, 4 H, β-CH2), 2.03–1.96 (m, 4 H, β-CH2), 1.49–1.22
(m, 32 H, 16 CH2), 0.83 (t, 3JH,H = 7.0 Hz, 12 H, 4 CH3).
13C NMR (150 MHz, CDCl3, 27.0 °C): δ = 166.7, 149.8, 148.5,
136.4, 132.0, 131.9, 129.8, 128.9, 128.5, 127.3, 127.2, 126.2, 123.6,
115.6, 55.4, 32.3, 31.8, 29.3, 27.1, 22.6, 14.0.
Fluorescence (CHCl3) : λmax (Irel) = 534.9 (1.00), 577.6 nm (0.50).
Fluorescence quantum yield (CHCl3, λexc = 491 nm, E491 nm, 1 cm
0.0147, reference A with Φ = 1.00): 0.95.
=
3
3
Fluorescence
quantum
yield
(CHCl3,
λexc = 350 nm,
E350 nm, 1 cm = 0.0035, reference: C with Φ = 1.00): 0.85.
Anal. Calcd for C49H42N4O5 (766.3): C, 76.74; H, 5.52; N, 7.31.
Found: C, 76.44; H, 5.63; N, 7.26.
2-[4-(2,1,3-Benzothiadiazol-4-yl)phenyl]-9-(nonadecan-10-yl)an-
thra[2,1,9-def:6,5,10-d′e′f′]diisoquinoline-1,3,8,10(2H,9H)-
tetraone (6b)
MS (DEP/EI): m/z (%) = 1042 (6) [M+ + H ], 678 (100) [M+ + H –
Following the typical procedure for 6a using 3c (45 mg,
0.20 mmol), 9-(1-nonyldecyl)-1H-isochromeno[6′,5′,4′:10,5,6]an-
thra[2,1,9-def]isoquinoline-1,3,8,10(9H)-tetraone (5b; 132 mg,
200 μmol), Zn(OAc)2 (7.4 mg, 40 μmol), and quinoline (2.5 mL) to
give 6b as an amorphous red material; yield: 128 mg (74%); mp
278–281 °C (dec.); Rf = 0.3 (silica gel, CH2Cl2).
2·C13H26].
HRMS: m/z [M + H]+ calcd for C66H68N5O7: 1042.5041; found:
1042.5070.
UV/Vis (CHCl3): λmax (ε) = 315.9 (23400), 330.7 (23500), 381.2
(40900), 411.6 (15700), 436.8 (37300), 467.3 nm (57100).
IR (ATR): 2921 (m), 1695 (s), 1650 (s), 1593 (s), 1342 (s), 1253 (s),
864 (m), 810 (s), 793 (s), 746 cm–1 (s).
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 8.77–8.63 (m, 8 H,
Fluorescence (CHCl3): λmax (Irel) = 476.3 (1.00), 511.2 nm (0.80).
Fluorescence quantum yield (CHCl3, λexc = 437 nm, E437 nm, 1 cm
0.0152, reference B with Φ = 1.00): 0.12.
=
=
3
H
per), 8.17 (d, JH,H = 8.4 Hz, 2 H, Harom), 8.04 (dd, 3JH,H = 8.7 Hz,
Fluorescence quantum yield (CHCl3, λexc = 350 nm, E350 nm, 1 cm
0.0109, reference C with Φ = 1.00): 0.12.
4JH,H = 1.0 Hz, 1 H, Harom), 7.79 (dd, 3JH,H = 6.9 Hz, 4JH,H = 1.0 Hz,
3
3
1 H, Harom), 7.72 (dd, JH,H = 6.9 Hz, JH,H = 8.7 Hz, 1 H, Harom),
7.52 (d, 3JH,H = 8.4 Hz, 2 H, Harom), 5.21–5.15 (m, 1 H, CH), 2.28–
2.20 (m, 2 H, β-CH2), 1.90–1.82 (m, 2 H, β-CH2), 1.38–1.13 (m,
28 H, 14 CH2), 0.82 (t, 3JH,H = 7.1 Hz, 6 H, 2 CH3).
Anal. Calcd for C66H67N5O7 (1041.5): C, 76.06; H, 6.48; N, 6.72.
Found: C, 75.89; H, 6.43; N, 6.70.
2-(4,7-Dibromo-2,1,3-benzothiadiazol-5-yl)-9-(1-hexylhep-
tyl)anthra[2,1,9-def:6,5,10-d′e′f′]diisoquinoline-
1,3,8,10(2H,9H)-tetraone (15; Figure 9)
13C NMR (150 MHz, CDCl3, 27.0 °C): δ = 163.6, 155.6, 153.4,
137.8, 135.2, 134.3, 133.6, 131.9, 130.3, 129.9, 129.6, 128.8, 128.1,
126.7, 126.4, 123.3, 123.3, 123.1, 120.9, 54.8, 32.3, 31.8, 29.5,
29.3, 27.0, 22.6, 14.1.
MS (DEP/EI): m/z (%) = 866 (11) [M+], 600 (100) [M+ – C19H38].
HRMS: m/z [M]+ calcd for C55H54N4O4S: 866.3866; found:
O
N
O
O
Br
N
N
N
S
866.3863.
O Br
UV/Vis (CHCl3): λmax (ε) = 315.9 (19300), 351.1 (12100), 459.8
(21000), 491.0 (55800), 527.4 nm (92500).
15
Figure 9
Fluorescence (CHCl3): λmax (Irel) = 534.6 (1.00), 577.5 (0.50), 625.5
nm (0.12).
Following the typical procedure for 6c using 4,7-dibromo-2,1,3-
benzothiadiazol-5-amine (63 mg, 0.20 mmol), 5a (115 mg,
200 μmol), Zn(OAc)2 (7.4 mg, 40 μmol), and quinoline (2.0 mL)
and then purification by dissolving the material in the minimal
amount of CH2Cl2 and purification by column chromatography
(short column with neutral alumina, CH2Cl2–MeOH, 100:1 and a
further column with silica gel, CH2Cl2, deeply red first fraction) to
Fluorescence quantum yield (CHCl3, λexc = 491 nm, E491 nm, 1 cm
0.0129, reference A with Φ = 1.00): 1.00.
=
Fluorescence
quantum
yield
(CHCl3,
λexc = 353 nm,
E353 nm, 1 cm = 0.0024, reference C with Φ = 1.00): 1.00.
Anal. Calcd for C55H54N4O4S (866.4): C, 76.18. 6.28; N, 6.46; S,
3.70. Found: C, 75.62; H, 6.26; N, 6.41; S, 3.54.
Synthesis 2012, 44, 3465–3477
© Georg Thieme Verlag Stuttgart · New York

PAPER
Benzothiadiazoloperylenes and Benzoxadiazoloperylenes
3475
give the product as a red solid; yield: 119 mg (69%); mp 185 °C
(dec.); Rf = 0.6 (CH2Cl2).
purification by column chromatography (basic alumina, CHCl3–
MeOH, 80:1, first brightly yellow shining main fraction) gave 9d as
a yellow solid; yield: 80 mg (77%); mp >300 °C; Rf = 0.3 (CH2Cl2).
IR (ATR): 2923 (w), 1655 (s), 1592 (s), 1339 (s), 1250 (s), 853 (m),
810 (s), 802 (m), 746 (s), 728 cm–1 (m).
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 8.80–8.67 (m, 8 H,
Hper), 7.90 (s, 1 H, Harom), 5.22–5.16 (m, 1 H), 2.29–2.21 (m, 2 H),
1.93–1.84 (m, 2 H), 1.39–1.19 (m, 16 H), 0.83 (t, 3J = 7.0 Hz, 6 H).
13C NMR (150 MHz, CDCl3, 27.0 °C): δ = 162.4, 153.2, 152.8,
136.9, 135.9, 134.0, 133.3, 132.3, 131.9, 131.2, 130.2, 129.5, 126.9,
126.3, 123.7, 123.1, 122.4, 115.8, 114.1, 54.9, 32.4, 31.7, 29.2,
26.9, 22.6, 14.0.
IR (ATR): 3077 (w), 2924 (m), 1705 (m), 1659 (s), 1365 (s), 1318
(s), 846 (m), 812 (m), 748 cm–1 (m).
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 10.56–10.48 (m,
3
2 H,
H
bper), 9.41 (d, JH,H = 8.4 Hz, 2 H, Hbper), 9.34 (dd,
4JH,H = 2.5 Hz, JH,H = 0.4 Hz, 1 H, Harom), 9.25–9.15 (m, 2 H,
Hbper), 8.76 (dd, 3JH,H = 8.2 Hz, 4JH,H = 2.5 Hz, 1 H, Harom), 7.95 (d,
3JH,H = 8.1 Hz, 1 H, Harom), 7.95 (d, 3JH,H = 6.4 Hz, 1 H, Harom), 7.80
(d, 3JH,H = 6.4 Hz, 1 H, Harom), 7.63 (dd, 3JH,H = 6.6 Hz, 3J = 9.0 Hz,
1 H, Harom), 5.15–5.27 (m, 2 H, CH), 2.40–2.28 (m, 4 H, β-CH2),
2.01–1.91 (m, 4 H, β-CH2), 1.46–1.17 (m, 32 H, 16 CH2), 0.81 (t,
3JH,H = 7.1 Hz, 12 H, 4 CH3).
5
MS (DEP/EI): m/z (%) = 862 (9) [M+], 602 (100) [M+ – C13H26
–
Br].
HRMS: m/z [M]+ calcd for C43H36Br2N4O4S: 862.0824; found:
862.0826.
13C NMR (150 MHz, CDCl3, 27.0 °C): δ = 166.2, 149.7, 148.6,
148.3, 146.1, 138.5, 132.9, 131.7, 131.1, 129.0, 127.8, 127.6, 126.8,
126.4, 124.8, 123.9, 123.0, 122.3, 116.6, 55.4, 32.4, 31.8, 29.3,
27.1, 22.6, 14.0.
UV/Vis (CHCl3): λmax (ε) = 306.6 (13700), 315.9 (16600), 352.0
(8000), 367.8 (7500), 461.3 (19200), 492.5 (53300), 528.8 nm
(88700).
MS (DEP/EI): m/z (%) = 1042 (10) [M+], 861 (45) [M+ + 1 –
C13H26], 679 (100) [M+ – 2·C13H26].
Fluorescence (CHCl3): λmax (Irel) = 537.3 (1.00), 579.7 nm (0.52).
HRMS: m/z [M]+ calcd for C65H66N6O7: 1042.4993; found:
1042.4981.
Fluorescence quantum yield (CHCl3, λexc = 492 nm, E492 nm, 1 cm
0.0137, reference A with Φ = 1.00): 0.94.
=
=
UV/Vis (CHCl3): λmax (ε) = 330.4 (26900), 380.4, (49000), 410.9
(16200), 436.8 (38500), 467.3 nm (59400).
Fluorescence quantum yield (CHCl3, λexc = 492 nm, E492 nm, 1 cm
0.0137, reference C with Φ = 1.00): 0.96.
Fluorescence (CHCl3) : λmax (I) = 477.2 (1.00), 510.6 nm (0.73).
Anal. Calcd for C43H36Br2N4O4S (862.1): C, 59.73; H, 4.20; N,
6.48; S, 3.71. Found: C, 59.48; H, 4.30; N, 6.42; S, 3.76.
Fluorescence quantum yield (CHCl3, λexc = 436 nm, E436 nm, 1 cm
0.0242, reference C with Φ = 1.00): 0.25.
=
=
6-[4-(2,1,3-Benzoxadiazol-4-yl)phenyl]-2,10-bis(1-hexylheptyl)-
1H-pyrrolo[3′4′:4,5]pyreno[2,1,10-def:7,8,9-d′e′f′]diisoquino-
line-1,3,5,7,9,11(2H,6H,10H)-hexone (9b)
Fluorescence quantum yield (CHCl3, λexc = 443 nm, E443 nm, 1 cm
0.0183, reference B with Φ = 1.00): 0.24.
Following the typical procedure for 10a using 4-(2,1,3-benzoxadia-
zol-4-yl)aniline (3d; 21 mg, 0.10 mmol), 8a (85 mg, 0.10 mmol),
and quinoline (1.8 mL) gave 9b as a yellow solid; yield: 77 mg
(74%); mp >300 °C; Rf = 0.7 (CH2Cl2).
Anal. Calcd for C65H66N6O7 (1042.5): C, 74.83; H, 6.38; N, 8.06;
found: C, 74.97; H, 6.60; N, 7.91.
6-(5-(2,1,3-Benzothiadiazol-4-yl)pyridin-2-yl)-2,10-bis(1-hexyl-
heptyl)-1H-pyrrolo[3′4′:4,5]pyreno[2,1,10-def:7,8,9-d′e′f′]di-
isoquinoline-1,3,5,7,9,11(2H,6H,10H)-hexone (9c)
Following the typical procedure for 10a using 3e (23 mg,
0.10 mmol), 8a (94 mg, 0.11 mmol), and quinoline (1.0 mL) at 210
°C for 3 h with purification by column chromatography (basic alu-
mina, CHCl3–MeOH, 80:1, first brightly yellow shining main frac-
tion) gave 9c as a yellow solid; yield: 79 mg (75%); mp >300 °C;
Rf = 0.3 (CH2Cl2).
IR (ATR): 3077 (w), 2924 (m), 1712 (s), 1662 (s), 1375 (s), 1364
(s), 1308 (s), 846 (w), 811 (s), 747 cm–1 (m).
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 10.37–10.23 (m,
2 H, Hbper), 9.19– 9.03 (m, 4 H, Hbper), 8.32 (d, 3JH,H = 8.6 Hz, 2 H,
H
arom), 7.98 (d, 3JH,H = 8.4 Hz, 2 H, Harom), 7.87 (dd, 3JH,H = 9.0 Hz,
4JH,H = 0.5 Hz, 1 H, Harom), 7.75 (d, 3JH,H = 6.3 Hz, 1 H, Harom), 7.58
(dd, JH,H = 6.6 Hz, 3JH,H = 9.0 Hz, 1 H, Harom), 5.32–5.26 (m, 2 H,
3
CH), 2.41–2.31 (m, 4 H, β-CH2), 2.03–1.95 (m, 4 H, β-CH2), 1.50–
IR (ATR): 3082 (w), 2926 (m), 1718 (s), 1705 (s), 1661 (s), 1366
(s), 1319 (s), 851 (m), 812 (s), 749 cm–1 (m).
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 10.51–10.39 (m,
1.22 (m, 32 H, 16 CH2), 0.82 (t, 3JH,H = 7.1 Hz, 12 H, 4 CH3).
13C NMR (150 MHz, CDCl3, 27.0 °C): δ = 166.7, 149.9, 148.5,
135.0, 132.6, 132.2, 131.8, 129.5, 129.2, 128.5, 127.4, 127.0, 126.6,
124.4, 123.7, 122.8, 115.6, 55.4, 32.4, 31.8, 29.3, 27.1, 22.6, 14.0.
MS (DEP/EI): m/z (%) = 1042 (6) [M+ + H], 678 (100) [M+ + H –
2·C13H26].
HRMS: m/z [M + H]+ calcd for C66H68N5O7: 1042.5041; found:
1042.5070.
2 H, Hbper), 9.33–9.29 (m, 3 H, Hbper, Harom), 9.22–9.12 (m, 2 H,
H
bper), 8.76 (dd, 3JH,H = 8.1 Hz, 4JH,H = 2.5 Hz, 1 H, Harom), 8.14 (dd,
4
3
3JH,H = 8.8 Hz, JH,H = 1.0 Hz, 1 H, Harom), 8.01 (d, JH,H = 8.1 Hz,
3
4
1 H, Harom), 7.91 (dd, JH,H = 6.8 Hz, JH,H = 0.9 Hz, 1 H, Harom),
7.80 (dd, 3JH,H = 6.8 Hz, 3JH,H = 8.8 Hz, 1 H, Harom), 5.37–5.26 (m,
2 H), 2.43–2.29 (m, 4 H, β-CH2), 2.03–1.92 (m, 4 H, β-CH2), 1.49–
1.19 (m, 32 H, 16 CH2), 0.83 (t, 3JH,H = 7.1 Hz, 12 H, 4 CH3).
UV/Vis (CHCl3): λmax (ε) = 330.7 (26600), 381.2 (39600), 410.1
(19400), 436.8 (37600), 467.3 nm (56500).
13C NMR (150 MHz, CDCl3, 27.0 °C): δ = 166.4, 155.6, 153.2,
149.5, 145.4, 139.2, 133.2, 133.1, 130.1, 129.6, 128.3, 128.0, 127.6,
127.0, 124.9, 124.0, 123.2, 121.9, 55.3, 32.4, 31.8, 29.3, 27.0, 22.6,
14.0.
Fluorescence (CHCl3): λmax (Irel) = 475.4 (1.00), 506.4 nm (0.79).
Fluorescence quantum yield (CHCl3, λexc = 437 nm, E437 nm, 1 cm
0.0241, reference C with Φ = 1.00): < 0.01.
=
MS (DEP/EI): m/z (%) = 1059 (9) [M+ + H], 877 (32) [M+ + H –
Anal. Calcd for C66H67N5O7 (1041.5): C, 76.06; H, 6.48; N, 6.72.
Found: C, 75.93; H, 6.49; N, 6.73.
C13H26], 695 (79) [M+ + H – 2·C13H26].
HRMS: m/z [M – H]+ calcd for C65H65N6O6S: 1057.4686; found:
1057.4731.
6-[5-(2,1,3-Benzoxadiazol-4-yl)pyridin-2-yl)-2,10-bis(1-hexyl-
heptyl)-1H-pyrrolo[3′4′:4,5]pyreno[2,1,10-def:7,8,9-d′e′f′]di-
isoquinoline-1,3,5,7,9,11(2H,6H,10H)-hexone (9d)
Following the typical procedure for 10a using 3f (21 mg,
0.10 mmol), 8a (85 mg, 0.10 mmol), and quinoline (1.8 mL) with
UV/Vis (CHCl3): λmax (ε) = 265.0 (38200), 315.6 (33400), 380.0,
(44900), 410.8 (17000), 437.0 (39400), 467.0 nm (59200).
Fluorescence (CHCl3): λmax (Irel) = 476.3 (1.00), 509.7 nm (0.75).
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 3465–3477

3476
H. Langhals et al.
PAPER
Fluorescence quantum yield (CHCl3, λexc = 437 nm, E437 nm, 1 cm
0.0352, reference C with Φ = 1.00): 0.27.
=
=
References
(1) (a) Brabec, C. J.; Sariciftci, N. S.; Hummelen, J. C. Adv.
Funct. Mater. 2001, 11, 15. (b) Günes, S.; Neugebauer, H.;
Sariciftci, N. S. Chem. Rev. 2007, 107, 1324. (c) Grätzel, M.
Nature (London) 2001, 414, 338. (d) Choi, H.; Kim, S.;
Kang, S. O.; Ko, J.; Kang, M.-S.; Clifford, J. N.; Forneli, A.;
Palomares, E.; Nazeeruddin, M. K.; Grätzel, M. Angew.
Chem. Int. Ed. 2008, 47, 8259; Angew. Chem. 2008, 120,
8283. (e) Gao, F.; Wang, Y.; Shi, D.; Zhang, J.; Wang, M.;
Jing, X.; Humphry-Baker, R.; Wang, P.; Zakeeruddin, S. M.;
Grätzel, M. J. Am. Chem. Soc. 2008, 130, 10720. (f) Gust,
D.; Moore, T. A.; Moore, A. L. Acc. Chem. Res. 2001, 34,
40. (g) Wasielewski, M. R. J. Org. Chem. 2006, 71, 5051.
(2) Reviews: (a) Langhals, H. Helv. Chim. Acta 2005, 88, 1309.
(b) Langhals, H. Heterocycles 1995, 40, 477. (c) Langhals,
H. Molecular Devices. Chiral, Bichromophoric Silicones:
Ordering Principles in Complex Molecules, In Silicon Based
Polymers; Ganachaud, F.; Boileau, S.; Boury, B., Eds.;
Springer: Netherlands, 2008, Chap. 1, 51–63.
(3) For recent contributions, see: (a) Würthner, F.; Stolte, M.
Chem. Commun. 2011, 47, 5109. (b) Osswald, P.; Reichert,
M.; Bringmann, G.; Würthner, F. J. Org. Chem. 2007, 72,
3403. (c) You, C.-C.; Hippius, C.; Gruene, M.; Würthner, F.
Chem.–Eur. J. 2006, 12, 7510. (d) Hiramoto, M.; Fukusumi,
H.; Yokoyama, M. Appl. Phys. Lett. 1992, 61, 2580.
(e) Zhan, X.; Facchetti, A.; Barlow, S.; Marks, T. J.; Ratner,
M. A.; Wasielewski, M. R.; Marder, S. R. Adv. Mater.
(Weinheim, Ger.) 2011, 23, 268. (f) Zhao, Y.; Wasielewski,
M. R. Tetrahedron Lett. 1999, 40, 7047. (g) Oesterling, I.;
Muellen, K. J. Am. Chem. Soc. 2007, 129, 4595. (h) Chen,
Z.; Zheng, Y.; Yan, H.; Facchetti, A. J. Am. Chem. Soc.
2009, 131, 8.
Fluorescence quantum yield (CHCl3, λexc = 437 nm, E437 nm, 1 cm
0.0352, reference B with Φ = 1.00): 0.26.
Anal. Calcd for C65H66N6O6S (1058.5): C, 73.70; H, 6.28; N, 7.93;
S, 3.03. Found: C, 73.72; H, 6.37; N, 7.80; S, 3.08.
8-[4-(2,1,3-Benzothiadiazol-4-yl)phenyl]-2-(1-hexylheptyl)-1H-
benzo[5,10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (14)
Dry LiCl (42 mg, 1.0 mmol), Mg (24 mg, 1.0 mmol), and dry ZnCl2
(136 mg, 1.00 mmol) in anhyd THF (2 mL) under argon were treat-
ed with 4-(4-iodophenyl)-2,1,3-benzothiadiazole (3h; 169 mg,
268 μmol) and the mixture was stirred at 20 °C for 2 h. The soln was
separated from the residual Mg (argon atmosphere), treated with a
mixture of Pd(dba)2 (6 mg, 10 μmol), (furyl)3P (5 mg, 22 μmol),
and 8-iodo-2-(1-hexylheptyl)-1H-benzo[5,10]anthra[2,1,9-def]iso-
quinoline-1,3(2H)-dione (13; 120 mg, 191 μmol) in anhyd THF
(1 mL), and stirred at 20 °C for 1 h. The reaction was quenched by
the addition of sat. aq NH4Cl soln (10 mL) and extracted with
CH2Cl2 (3 × 30 mL). The combined extracts were dried (MgSO4),
and evaporated in vacuo. The residue was dissolved in the minimal
amount of CHCl3–MeOH (80:1) and purified by column chroma-
tography (short column neutral alumina, CHCl3–MeOH, 80:1, and
then silica gel, CHCl3 and finally silica gel, toluene, deep red band)
to give 14 as a red solid; yield: 14 mg (7%); mp 169–170 °C; Rf =
0.4 (silica gel, toluene).
IR (ATR): 2923 (m), 1687 (s), 1646 (s), 1353 (s), 1292 (m), 1202
(m), 853 (m), 807 (s), 751 cm–1 (s).
1H NMR (600 MHz, CDCl3, 27 °C, TMS): δ = 8.64–8.55 (m, 2 H,
H
H
per), 8.51 (d, 3JH,H = 7.9 Hz, 1 H, Hper), 8.48 (d, 3JH,H = 7.2 Hz, 1 H,
per), 8.45 (dd, 3JH,H = 6.7 Hz, 3JH,H = 8.1 Hz, 2 H, Hper), 8.14–8.10
(m, 3 H), 8.06 (dd, 3JH,4H = 8.7 Hz, 4JH,H = 1.1 Hz, 1 H, Harom), 7.82
3
(dd, JH,H = 6.9 Hz, JH,H = 1.1 Hz,
1 H, Harom), 7.75 (dd,
(4) Langhals, H.; Demmig, S.; Huber, H. Spectrochim. Acta
1988, 44A, 1189.
3JH,H = 6.9 Hz, JH,H = 8.7 Hz, 1 H, Harom), 7.71 (d, JH,H = 8.4 Hz,
3
3
3
2 H, Harom), 7.66 (d, JH,H = 7.7 Hz, 1 H, Harom), 7.61 (dd,
(5) (a) Langhals, H.; Kollefrath, R.; Lindner, J. Macromol. Rep.
1995, A32, 415. (b) Langhals, H.; Gold, J. J. Prakt. Chem.
1996, 338, 654. (c) Langhals, H.; Jona, W. Angew. Chem.
Int. Ed. 1998, 37, 952; Angew. Chem. 1998, 110, 998.
(6) (a) Saragi, T. P. I.; Spehr, T.; Siebert, A.; Fuhrmann-Lieker,
T.; Salbeck, J. Chem. Rev. 2007, 107, 1011. (b) Silaghi, S.
D.; Spehr, T.; Cobet, C.; Saragi, T. P. I.; Werner, C.;
Salbeck, J.; Esser, N. Appl. Phys. 2008, 103, 043503/1.
(7) (a) Zimdars, S.; Langhals, H.; Knochel, P. Synthesis 2011,
1302. (b) Zimdars, S. PhD Dissertation; Universität
München: Germany, 2011. (c) Zimdars, S. Diplomarbeit;
Universität München: Germany, 2007.
3JH,H = 7.5 Hz, 3JH,H = 8.3 Hz, 1 H, Harom), 5.23–5.18 (m, 1 H, CH),
2.29–2.23 (m, 2 H, β-CH2), 1.88–1.83 (m, 2 H, β-CH2), 1.38–1.18
(m, 16 H, 8 CH2), 0.82 (t, 3JH,H = 7.1 Hz, 6 H, 2 CH3).
13C NMR (150 MHz, CDCl3, 27.0 °C): δ = 165.3, 164.2, 155.6,
153.5, 142.6, 140.0, 137.0, 133.9, 132.6, 130.8, 130.3, 130.0, 129.7,
129.5, 129.4, 129.1, 128.8, 128.4, 128.2, 127.9, 127.6, 127.0, 126.6,
123.3, 120.9, 129.6, 120.3, 120.1, 54.4, 32.4, 31.8, 29.3, 27.0, 22.6,
14.0.
MS (DEP/EI): m/z (%) = 713 (48) [M+], 531 (100) [M+ – C13H26].
HRMS: m/z [M]+ calcd for C47H43N3O2S: 713.3076; found:
713.3082.
(8) (a) Clososki, G. C.; Rohbogner, C. J.; Knochel, P. Angew.
Chem. Int. Ed. 2007, 46, 7681. (b) Rohbogner, C. J.;
Clososki, G. C.; Knochel, P. Angew. Chem. Int. Ed. 2008,
47, 1503.
UV/Vis (CHCl3): λmax (ε) = 315.9 (15700), 356.7 (8700), 502.1
(40200), 518.5 nm (40200).
Fluorescence (CHCl3): λmax = 569.0 nm.
(9) Barder, T. E.; Buchwald, S. L. Org. Lett. 2004, 6, 2649.
(10) Farina, V.; Krishnan, B. J. Am. Chem. Soc. 1991, 113, 9585.
(11) (a) Foerster, T. Naturwissenschaften 1946, 33, 166; Chem.
Abstr. 1947, 41, 36668. (b) Foerster, T. Ann. Phys. 1948, 2,
55; Chem. Abstr. 1949, 43, 31172. (c) Foerster, T. Z.
Elektrochem. 1949, 53, 93; Chem. Abstr. 1949, 43, 33629.
(d) Foerster, T. Z. Naturforsch. A 1949, 4, 321; Chem. Abstr.
1950, 44, 43074.
Fluorescence quantum yield (CHCl3, λexc = 498 nm, E498 nm, 1 cm
0.0235, reference A with Φ = 1.00): 1.00.
=
=
Fluorescence quantum yield (CHCl3, λexc = 498 nm, E498 nm, 1 cm
0.0235, reference C with Φ = 1.00): 1.00.
Anal. Calcd for C47H43N3O2S (713.3): C, 79.07; H, 6.07; N, 5.89; S,
4.49. Found: C, 78.80; H, 6.10; N, 5.74; S, 4.82.
(12) Langhals, H.; Esterbauer, A. J.; Walter, A.; Riedle, E.;
Pugliesi, I. J. Am. Chem. Soc. 2010, 132, 16777.
(13) Langhals, H.; Karolin, J.; Johansson, L. B.-Å. J. Chem. Soc.,
Faraday Trans. 1998, 94, 2919.
(14) Kalinin, S.; Speckbacher, M.; Langhals, H.; Johansson, L.
B.-Å. Phys. Chem. Chem. Phys. 2001, 3, 172.
Acknowledgment
This work was supported by the Dr. Römer prize, by the CIPSM
cluster in Munich and the DFG (LMUexcellent) with financial sup-
port.
Synthesis 2012, 44, 3465–3477
© Georg Thieme Verlag Stuttgart · New York