Synthesis and electronic and photophysical properties of [2.2]- and [3.3]paracyclophane-based donor-donor′-acceptor triads

Article abstract of DOI:10.1021/jo5020273

Three types of the donor(D)-donor′(D′)-acceptor(A) triads 1-6 with different D-A combinations, carbazole (Cz, D)-[n.n]PCP(D′)-1,8-naphthalimide (NI, A) (1-3), 10H-phenothiazine (PTZ, D)-[n.n]PCP(D′)-NI(A) (4, 5), and 10-methyl-10H-phenothiazine (Me-PTZ, D)-[2.2]PCP-2,1,3-benzothiadiazole (BTD, A) 6, were synthesized for the elucidation of their photophysical properties. The absorption spectra and electrochemical properties indicated that the chromophores (D, D′, and A) do not interact with each other in the ground state. Cz-(CH₂)₃-[2.2]PCP-(CH₂)₃-NI 1 and Cz-(CH₂)₃-[3.3]PCP-(CH₂)₃-NI 2 show an exciplex emission between the PCP and NI moieties in cyclohexane and the intensity of the band is much higher in 2 than in 1, whereas Cz-(CH₂)₂-[2.2]PCP-(CH₂)₂-NI 3 does not show any exciplex emission in cyclohexane. These results indicated that the combination of [3.3]PCP and a trimethylene chain is preferable for the exciplex formation. PTZ-(CH₂)₃-[2.2]PCP-(CH₂)₃-NI 4 shows a broad band at 519 nm in cyclohexane, which is associated with the formation of the exterplex band among the NI, [2.2]PCP, and PTZ moieties, while PTZ-(CH₂)₃-[3.3]PCP-(CH₂)₃-NI 5 does not show the band. Me-PTZ-(CH₂)₂-[2.2]PCP-(CH₂)₂-BTD 6 shows a broad fluorescence band due to both the BTD and PTZ moieties in cyclohexane. In CH₃CN, the fluorescence spectra of 1-6 suggest the presence of a photoinduced charge separation process. The study of the photoinduced charge separation process will be soon reported elsewhere.

Full text of DOI:10.1021/jo5020273

Article
pubs.acs.org/joc
Synthesis and Electronic and Photophysical Properties of [2.2]- and
¶
[
3.3]Paracyclophane-Based Donor−Donor′−Acceptor Triads
†,‡ § †,‡ ∥
†
Takaaki Miyazaki, Masahiko Shibahara, Jun-ichi Fujishige, Motonori Watanabe, Kenta Goto,
,†
and Teruo Shinmyozu*
†
‡
Institute for Materials Chemistry and Engineering (IMCE), Department of Chemistry, Graduate School of Sciences, Kyushu
University, Hakozaki 6-10-1, Fukuoka 812-8581, Japan
§
Department of Chemistry, Faculty of Education and Welfare Science, Oita University, Dannoharu 700, Oita 870-1192, Japan
∥International Institute for Carbon-Neutral Energy Research (I2CNER), Kyushu University, Motooka 744, Nishi-ku, Fukuoka
819-0395, Japan
*
S Supporting Information
ABSTRACT: Three types of the donor(D)−donor′(D′)−acceptor(A)
triads 1−6 with different D−A combinations, carbazole (Cz, D)-
[n.n]PCP(D′)-1,8-naphthalimide (NI, A) (1-3), 10H-phenothiazine
(PTZ, D)-[n.n]PCP(D′)-NI(A) (4, 5), and 10-methyl-10H-phenothiazine
(Me-PTZ, D)-[2.2]PCP-2,1,3-benzothiadiazole (BTD, A) 6, were synthe-
sized for the elucidation of their photophysical properties. The absorption
spectra and electrochemical properties indicated that the chromophores (D,
D′, and A) do not interact with each other in the ground state. Cz-(CH ) -
2
3
[
2.2]PCP-(CH ) -NI 1 and Cz-(CH ) -[3.3]PCP-(CH ) -NI 2 show an
2 3 2 3 2 3
exciplex emission between the PCP and NI moieties in cyclohexane and the
intensity of the band is much higher in 2 than in 1, whereas Cz-(CH ) -
2
2
[
2.2]PCP-(CH ) -NI 3 does not show any exciplex emission in
2 2
cyclohexane. These results indicated that the combination of [3.3]PCP
and a trimethylene chain is preferable for the exciplex formation. PTZ-
(
CH ) -[2.2]PCP-(CH ) -NI 4 shows a broad band at 519 nm in cyclohexane, which is associated with the formation of the
2 3 2 3
exterplex band among the NI, [2.2]PCP, and PTZ moieties, while PTZ-(CH ) -[3.3]PCP-(CH ) -NI 5 does not show the band.
2
3
2 3
Me-PTZ-(CH ) -[2.2]PCP-(CH ) -BTD 6 shows a broad fluorescence band due to both the BTD and PTZ moieties in
2
2
2 2
cyclohexane. In CH CN, the fluorescence spectra of 1−6 suggest the presence of a photoinduced charge separation process. The
3
study of the photoinduced charge separation process will be soon reported elsewhere.
1
. INTRODUCTION
As the first report of our continued efforts to elucidate the
properties of the multilayered [2.2]- and [3.3]PCP-based
molecular wires with acceptor and donor moieties at the
terminals, we reported the syntheses and photophysical
properties of the two- and three-layered [3.3]PCP-based D−A
systems, in which an external benzene ring of the two- and three-
layered [3.3]PCPs is replaced with 2,1,3-benzothiadizole (BTD)
as an acceptor. In both D−A systems, the charge transfer (CT)
absorption bands appeared in the longest wavelength region, and
the broad fluorescence bands were attributed to the intra-
molecular exciplex emission. Their redox properties also support
the strong electronic interaction between D and A in the ground
state. In order to decrease the magnitude of the electronic
interaction between D and A in the ground state, we designed a
way to connect the D and A moieties at the terminals of the
multilayered [2.2]- and [3.3]PCPs, respectively, by single
oligomethylene spacers. Thus, we planned to synthesize a series
Molecular wires have been intensively studied as an electron
1
,2
and/or hole conducting material. The molecular wire as a
donor (D)−bridge (B)−acceptor (A) (D−B−A) system has
served as a suitable model compound for the elucidation of the
electron and/or hole transfer in molecular arrays. Molecular
wires are mainly divided into two types, a linear π-conjugated
array and a π-stack array. DNA has been most intensively
studied as a model compound for the π-stack type molecular
wires. In DNA, a charge transport mechanism and the multistep
hopping mechanism have been proposed. Multilayered [2.2]-
and [3.3]paracyclophanes (PCPs) have the potential to be a
reference of the DNA base pairs as the bridge because the
transannular distances of the benzene rings (ca. 3.0−3.3 Å) are
similar to those (ca. 3.4 Å) of the base pairs of the double-strand
structure of DNA. In addition, efficient charge delocalization
over the [3.3]PCPs was observed in the radical cation species of
the two- to four-layered [3.3]PCPs based on a pulse radiolysis
1a
3
−8
9,10
9
11
1
2
study. A limited number of the D-B-A systems containing PCPs
as a bridge has already been reported.
Received: September 3, 2014
13,14
©
XXXX American Chemical Society
A
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Figure 1. Synthesized D−D′−A triads 1−6 containing the [2.2]- or [3.3]PCP moiety as the bridge with electron donating ability (D′).
Scheme 1. Syntheses of Cz-(CH ) -[2.2]PCP-(CH ) -NI 1 and Cz-(CH ) -[3.3]PCP-(CH ) -NI 2 as well as PTZ-(CH ) -
2
3
2 3
2 3
2 3
2 3
a
[
2.2]PCP-(CH ) -NI 4 and PTZ-(CH ) -[3.3]PCP-(CH ) -NI 5
2 3 2 3 2 3
a
n
Reagents and conditions: (a) allylSn Bu , Pd(PPh ) , DMF, 100 °C, 1 d; (b) (1) 9-BBN/THF, 40 °C, 3 h, (2) 2 M NaOH aq., 30% H O aq., rt,
3
3
4
2
2
overnight; (c) CBr , PPh , CH Cl , rt, 3 h; (d) 1,8-naphthalimide, Cs CO , DMF, rt, overnight; (e) carbazole, n-Bu NBr, toluene, 2 M NaOH aq.,
4
3
2
2
2
3
4
reflux, 2 d; (f) 10H-phenothiazine, t-BuOK, DMF, rt, overnight.
of D-D′(multilayered PCP)-A systems for the study of the
dependence of the rate of charge transport on the D−A distance,
i.e., how a charge is transported through the benzene rings in the
multilayered PCP in the D−D′−A system. As the first step along
this line, we now report the syntheses, and electronic and
photophysical properties of the simplest triads in this series with
two-layered PCPs as the D′. The triads, which can be grouped
[2.2]PCP-(CH ) -2,1,3-benzothiadiazole (BTD, A) 6 (Figure
1).
2
2
On the basis of the detailed study of the absorption,
fluorescence, and transient absorption spectra of the triads 1−
6 along with their reference compounds, the dependence of the
electronic interaction between the A and D′ as well as D′and D
moieties in the photoexcited state on the length of the
oligomethylene linkers and the transannular distance of the
benzene rings should be elucidated. As a result, the photophysical
properties of the triads 1−6, such as the charge separation
process, should become clear by the analysis of the femto-second
transient absorption spectra of the triads and reference
compounds. In this paper, we report the syntheses, redox
15
into three types of the D−A combinations, carbazole (Cz, D) -
(
A)
1
(
CH ) -[n.n]PCP(D′)-(CH ) -1,8-naphthalimide (NI,
2
m
2 m
1
5a,d,16
(1: n = 2, m = 3; 2, n = 3, m = 3; 3, n = 2, m = 2),
1
7
0H-phenothiazine (PTZ, D) -(CH ) -[n.n]PCP (D′)-
2
m
CH ) -NI(A) (4: n = 2, m = 3; 5: n = 3, m = 3), as well as
2 m
1
0-methyl-10H-phenothiazine (Me-PTZ, D)-(CH ) -
2 2
B
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a
Scheme 2. Synthesis of Cz-(CH ) -[2.2]PCP-(CH ) -NI 3
2
2
2 2
a
n
Reagents and conditions: (a) vinylSn Bu , Pd(PPh ) , toluene, 100 °C, 1 d; (b) (1) 9-BBN/THF, 60 °C, overnight, (2) 2 M NaOH aq., 30% H O
2
3
3
4
2
aq., rt, 6 h; (c) CBr , PPh , CH Cl , rt, 3 h; (d) 1,8-naphthalimide, Cs CO , DMF, rt, overnight; (e) carbazole, n-Bu NBr, toluene, 2 M NaOH aq.,
4
3
2
2
2
3
4
reflux, 2 d.
a
Scheme 3. Synthesis of Me-PTZ-(CH ) -[2.2]PCP-(CH ) -BTD 6
2
2
2 2
a
Reagents and conditions: (a) 4-bromo-BTD, Pd(OAc) , n-Bu NBr, K CO , DMF, 100 °C, 2 d; (b) 3-bromo-Me-PTZ, Pd(dppf)Cl ·CH Cl , n-
2
4
2
3
2
2
2
Bu NBr, K CO , DMF, 100 °C 1 d; (c) NH NH ·H O, diethylene glycol, 100 °C, 20 h.
4
2
3
2
2
2
properties, and absorption and fluorescence spectra of the triads
−6, while the detailed discussion on the transient absorption
spectral study will be reported elsewhere.
room temperature provided Br(CH ) -[2.2]PCP-(CH ) -NI 11
2 3 2 3
(48%). Further N-alkylation of the Cz moiety by the bromide 11
1
in the presence of n-Bu NBr as a phase-transfer catalyst in
4
toluene and 2 M aqueous NaOH at reflux afforded the desired
2
. RESULTS AND DISCUSSION
triad 1 (quant.). The [3.3]PCP-based triad, Cz-(CH
2 3
) -
[
3.3]PCP-(CH ) -NI 2, was synthesized starting from 4,14-
2
3
Synthesis. The [2.2]PCP-based triad with carbazole (Cz) as
19
dibromo[3.3]PCP 12 by a similar series of reactions reported
for the synthesis of 1. The introduction of the PTZ moiety as a
donor into the NI-substituted [2.2]PCP derivative was achieved
by the reaction of the PTZ anion generated by t-BuOK in DMF
at room temperature with the bromide 11 to give the triad, PTZ-
a donor and 1,8-naphthalimide (NI) as an acceptor with
trimethylene linkers, Cz-(CH ) -[2.2]PCP-(CH ) -NI 1, was
synthesized from 4,12-dibromo[2.2]PCP 7, which was prepared
2
3
2 3
1
8
from [2.2]PCP according to the reported procedures in 5 steps
Scheme 1). The pseudo-para-substituted dibromide 7 was
reacted with allyltributyltin in the presence of Pd(PPh ) in DMF
(
(
CH ) -[2.2]PCP-(CH ) -NI 4 (28%). A similar N-alkylation of
2 3
the PTZ moiety with the bromide 16 afforded PTZ-(CH2)3-
2 3
3
4
at 100 °C to give 4,12-diallyl[2.2]PCP 8 (87%), which was
converted into the diol 9 by hydroboration with 9-
borabicyclo[3.3.1]nonane (9-BBN) in THF, followed by
oxidation with 30% aqueous H O under basic conditions. The
[3.3]PCP-(CH ) -NI 5 (59%).
2 3
The triad with the dimethylene linkers, Cz-(CH ) -[2.2]PCP-
2 2
14b
(
CH ) -NI 3, was synthesized from 4,12-divinyl[2.2]PCP 17,
2 2
2
2
diol 9 was brominated with CBr and PPh in CH Cl at room
which was derived from 4,12-dibromo[2.2]PCP 7 by the reaction
with vinyltributyltin in the presence of Pd(PPh in toluene at
4
3
2
2
temperature to give the dibromide 10 (96% from 8). The donor
and acceptor moieties were introduced into the [2.2]PCP
skeleton in a stepwise manner. N-alkylation of the NI moiety
with the dibromide 10 in the presence of Cs CO in DMF at
)
4 4
100 °C (56%). Hydroboration of 17, followed by bromination of
the resultant diol 18 afforded the dibromide 19. Stepwise
introduction of the NI and Cz moieties into the [2.2]PCP
2
3
C
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+
Table 1. Redox Potentials (V vs Fc/Fc ) and HOMO and LUMO Energies of 1−6, Me-Cz, Me-PTZ, Me-NI, BTD, [2.2]PCP, and
[
3.3]PCP in CH CN Containing 0.1 M n-Bu PF
3
4
6
Ered(I)/V
Eox1(I)/V
Eox2(I)/V
HOMO /eV
c
LUMO /eV
d
Egap/eV
a
b
Cz-(CH ) -[2.2]PCP-(CH ) -NI 1
−1.75
−1.75
−1.74
−1.71
−1.73
−1.93
+0.77
−5.57
−5.56
−5.54
−5.06
−5.06
−5.05
−5.54
−5.10
−3.05
−3.05
−3.06
−3.09
−3.07
−2.87
2.52
2.51
2.48
1.97
1.99
2.18
2
3
2 3
a
b
Cz-(CH ) -[3.3]PCP-(CH ) -NI 2
+0.76
2
3
2 3
a
b
Cz-(CH ) -[2.2]PCP-(CH ) -NI 3
+0.74
2
2
2 2
b
b
b
PTZ-(CH ) -[2.2]PCP-(CH ) -NI 4
+0.26
+0.90
2
3
2 3
b
b
b
PTZ-(CH ) -[3.3]PCP-(CH ) -NI 5
+0.26
+0.87
2
3
2 3
a
a
b
Me-PTZ-(CH ) -[2.2]PCP-(CH ) -BTD 6
+0.25
+0.84
2
2
2 2
b
Me-Cz
Me-PTZ
Me-NI
BTD
+0.74
a
b
+0.30
+0.91
a
−1.73
−1.89
−3.07
−2.91
a
b
[
2.2]PCP
3.3]PCP
+1.09
−5.89
−5.78
b
b
[
+0.98
+1.30
a
−1
b
The potential E(I) was determined by CV at the potential scan rate of 100 mV s . The potential E(I) was determined by DPV at the potential
scan rate of 20 mV s . HOMO = −4.8 − E (I). LUMO = −4.8 − E 1/2(I).
−1
c
ox
d
red
Figure 2. (a) Absorption spectra of Cz-(CH ) -[2.2]PCP-(CH ) -NI 1 (blue), Cz-(CH ) -[3.3]PCP-(CH ) -NI 2 (green), Cz-(CH ) -[2.2]PCP-
2
3
2
3
2
3
2
3
2 2
(
(
CH ) -NI 3 (light blue), PTZ-(CH ) -[2.2]PCP-(CH ) -NI 4 (red), PTZ-(CH ) -[3.3]PCP-(CH ) -NI 5 (purple), and Me-PTZ-(CH ) -[2.2]PCP-
2 2 2 3 2 3 2 3 2 3 2 2
CH ) -BTD 6 (orange) in CH Cl . (b) Absorption spectra of Me-NI (blue), Me-Cz (red), Me-PTZ (green), and Me-BTD (purple) in CH Cl .
2
2
2
2
2
2
skeleton by the successive N-alkylation reactions afforded the
desired triad 3 (Scheme 2).
references (Figures S1 and S2). The observed redox potentials
and the HOMO and LUMO energies estimated by the redox
The synthesis of the triad, Me-PTZ-(CH ) -[2.2]PCP-
potentials in CH CN are summarized in Table 1. The DFT
2
2
3
20
(
CH ) -BTD 6, was achieved from 4,12-divinyl[2.2]PCP 17
(B3LYP/6-31G* level) calculations (Gaussian 09) of the
HOMO and LUMO orbitals of 1, 2, and 3 indicated that their
LUMO orbitals are completely localized over the NI moiety,
while their HOMO orbitals are mostly localized over the Cz
moiety and partially localized over the [2.2]- or [3.3]PCP
moieties through the di- and trimethylene linkers. The
calculations also showed that the HOMO and LUMO orbitals
of 4, 5, and 6 are completely localized over the PTZ and NI or
BTD moieties, respectively (Figure S3). These results suggest
almost no orbital interaction between A and D′ as well as D and
D′ in the ground state.
2
2
according to the procedures shown in Scheme 3. An acceptor
moiety, BTD, and a donor moiety, Me-PTZ, were introduced
into the [2.2]PCP skeleton by the Heck coupling reaction in a
stepwise manner. The divinyl compound 17 was reacted with 4-
bromo-2,1,3-benzothiadiazole in the presence of Pd(OAc) , n-
2
Bu NBr, and K CO in DMF at 100 °C for 2 d to give the BTD-
4
2
3
substituted [2.2]PCP 21 (39%), which was further reacted with
-bromo-10-methyl-10H-phenothiazine in the presence of
Pd(dppf)Cl ·CH Cl , n-Bu NBr, and K CO in DMF at 100
3
2
2
2
4
2
3
°
(
C to afford the BTD- and Me-PTZ-tethered [2.2]PCP 22
59%). Finally, the olefinic double bonds of 22 were reduced
Cz-(CH ) -[2.2]PCP-(CH ) -NI 1 shows one reversible
2
3
2 3
red
with NH NH ·H O in diethylene glycol at 100 °C to give the
reduction process (E (I): −1.75 V) and one irreversible
oxidation process (E (I): +0.77 V), which was determined by
DPV, in CH CN containing 0.1 M n-Bu NPF vs Fc/Fc (Figure
2
2
2
ox
desired 6 as yellow crystals from a mixture of toluene and MeOH
41%).
Electrochemical Properties. For the evaluation of the
+
(
3
4
6
S1). Cz-(CH ) -[3.3]PCP-(CH ) -NI 2 and Cz-(CH ) -
2
3
2
3
2 2
magnitude of the electronic interaction between the chromo-
phores in the ground state, cyclic voltammetry (CV) and
differential pulse voltammetry (DPV) of 1−6 were measured in
[2.2]PCP-(CH ) -NI 3 also exhibited CV and DPV profiles
2 2
red
ox
similar to those of 1 (2, E (I): −1.75 V, E (I): +0.76 V; 3,
red
ox
21
E (I): −1.74 V, E (I): +0.74 V). The values of the redox
+
CH CN containing 0.1 M n-Bu NPF vs Fc/Fc along with Me-
potentials are in good agreement with those of the components,
Me-NI (E (I): −1.73 V) and Me-Cz (E (I): +0.74 V). PTZ-
3
4
6
red
ox
Cz, Me-PTZ, Me-NI, BTD, [2.2]PCP, and [3.3]PCP as
D
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The Journal of Organic Chemistry
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Table 2. Absorption Bands (λmax) and Molar Absorbance of 1−6, Me-NI, Me-Cz, Me-PTZ, and Me-BTD in CH Cl CH CN, and
2
2,
3
Cyclohexane
λmax/nm (log ε)
compound
CH Cl
CH CN
cyclohexane
2
2
3
Cz-(CH ) -[2.2]PCP-(CH ) - 236 (4.96), 265 (4.36), 295 (4.26),
230 (4.97), 263 (4.39), 294 (4.29),
332 (4.19), 346 (4.17)
231 (4.99), 236 (4.98), 263 (4.38), 294 (4.41),
330 (4.21), 345 (4.23)
2
3
2 3
NI 1
334 (4.20), 347 (4.18)
Cz-(CH ) -[3.3]PCP-(CH ) - 237 (4.94), 266 (4.38), 295 (4.28),
235 (4.90), 262 (4.34), 294 (4.22),
332 (4.17), 346 (4.15)
236 (4.91), 264 (4.30), 294 (4.33), 330 (4.16),
345 (4.17)
2
3
2 3
NI 2
334 (4.21), 347 (4.19)
Cz-(CH ) -[2.2]PCP-(CH ) - 232 (4.97), 264 (4.36), 295 (4.27),
230 (4.96), 263 (4.42), 294 (4.32),
331 (4.20), 346 (4.19)
230 (4.92), 261 (4.27), 295 (4.30), 330 (4.17),
345 (4.20)
2
2
2 2
NI 3
333 (4.24), 348 (4.22)
PTZ-(CH ) -[2.2]PCP-
233 (4.84), 257 (4.54), 333 (4.18),
348 (4.09)
231 (4.81), 256 (4.53), 331 (4.16),
343 (4.07)
232 (4.84), 256 (4.54), 326 (4.17), 345 (4.09)
2
3
(
CH ) -NI 4
2 3
a
a
PTZ-(CH ) -[3.3]PCP-
237 (4.81), 257 (4.55), 334 (4.20),
348 (4.11)
234, 256, 330, 345
236, 256, 326, 344
2
3
(
CH ) -NI 5
2 3
Me-PTZ-(CH ) -[2.2]PCP-
258 (4.61), 312 (4.24)
256 (4.67), 311 (4.26)
257 (4.71), 311 (4.33)
2
2
(
CH ) -BTD 6
2 2
Me-NI
Me-Cz
237 (4.67), 334 (4.08), 348 (4.03)
238 (4.60), 264 (4.36), 295 (4.20),
234 (4.65), 332 (4.05), 343 (4.01)
235 (4.67), 330 (4.03), 344 (4.03)
236 (4.64), 262 (4.35), 293 (4.19),
331 (3.54), 345 (3.57)
236 (4.67), 262 (4.32), 293 (4.64), 328 (3.60),
344 (3.74)
3
32 (3.56), 346 (3.60)
Me-PTZ
Me-BTD
255 (4.57), 310 (3.73)
305 (4.10), 312 (4.14)
255 (4.62), 311 (3.76)
303 (4.06), 310 (4.09)
253 (4.60), 309 (3.72)
304 (4.06), 310 (4.09)
a
Log ε was not determined due to the low solubility.
Figure 3. (a) Fluorescence spectra of Cz-(CH ) -[2.2]PCP-(CH ) -NI 1 (blue), Cz-(CH ) -[3.3]PCP-(CH ) -NI 2 (green), Cz-(CH ) -[2.2]PCP-
2
3
2
3
2
3
2
3
2 2
(
(
2
CH ) -NI 3 (light blue), PTZ-(CH ) -[2.2]PCP-(CH ) -NI 4 (red), PTZ-(CH ) -[3.3]PCP-(CH ) -NI 5 (purple) in cyclohexane (λ = 330 nm).
2
2
2
3
2
3
2
3
2
3
ex
b) Fluorescence spectra of Br(CH ) -[2.2]PCP-(CH ) -NI 11 (blue), Br(CH ) -[3.3]PCP-(CH ) -NI 16 (red), and Br(CH ) -[2.2]PCP-(CH ) -NI
2
3
2
3
2
3
2
3
2
2
2 2
0 (green) in cyclohexane (λ = 330 nm).
ex
(
(
5
CH ) -[2.2]PCP-(CH ) -NI 4 and PTZ-(CH ) -[3.3]PCP-
due to the effective transannular electronic interaction with the
[3.3]PCP moiety.
2
3
2 3
2 3
red
1a
CH ) -NI 5 show one reduction process (4, E (I): −1.71 V;
2
3
red
ox
, E (I): −1.73 V) and two oxidation processes (4, E (I):
0.26, +0.90 V; 5, E (I): +0.26, +0.87 V), corresponding to the
Absorption Spectra. The absorption spectra of the D−D′−
A triads 1−6, their components, Me-NI, Me-Cz, Me-PTZ, and
Me-BTD, as well as related reference compounds were measured
in CH Cl (Figure 2), and their λ and molar absorbance are
ox
+
ox
redox potentials of the NI and PTZ (Me-PTZ, E (I): +0.30,
0.91 V) moieties, respectively. Me-PTZ-(CH ) -[2.2]PCP-
+
2
2
2
2
max
(
CH ) -BTD 6 shows a reversible one-electron reduction
summarized in Table 2. Me-NI shows a broad structured
2
2
red
process (E (I): −1.93 V) and two oxidation processes
absorption band in the region of ca. 260−360 nm (λ = 334 and
max
ox
(E (I): +0.25, +0.84 V) in CH CN, and their potentials are
348 nm) along with a sharp absorption band at 237 nm above
220 nm, while Me-Cz exhibits broad structured absorption bands
3
red
quite similar to the reduction potential of BTD (E (I): −1.89
V) and the oxidation potential of Me-PTZ, respectively. These
results clearly indicated that the donor and acceptor moieties in
each of the compounds do not interact with each other and with
the [2.2]- or [3.3]PCP moiety in the ground state. As expected,
the connection of the D, D′, and A moieties with di- or
trimethylene linkers significantly decreases the magnitude of the
electronic interaction between the neighboring chromophores,
and this is in sharp contrast to the reduction potential of the BTD
moiety incorporated into the [3.3]PCP moiety in the two- and
three-layered [3.3]PCP-based D−A diads, in which the BTD
moiety shows higher reduction potentials than that of BTD itself
in the region of ca. 310−350 nm (λ = 332 and 346 nm) and
max
three sharp absorption bands at 238, 264, and 295 nm (Figure
2b). Me-PTZ shows a sharp band at 255 nm and a broad
structureless band at ca. 310 nm above 230 nm, whereas Me-
BTD exhibits structured broad bands in the region of 270−320
nm (λ = ca. 310 nm). The Cz-(CH ) -[n.n]PCP-(CH ) -NI
max
2 m
2 m
triads, 1 (n = 2, m = 3), 2 (n = 3, m = 3), and 3 (n = 2, m = 2), show
quite similar absorption bands at 236, 265, and 295 nm as well as
in the region of ca. 310−360 nm, which are a superposition of
those of the components, Me-Cz and Me-NI. The PTZ-(CH ) -
2
3
[n.n]PCP-(CH ) -NI triads, 4 (n = 2) and 5 (n = 3), also show
2
3
E
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The Journal of Organic Chemistry
Article
Figure 4. (a) Fluorescence spectra of Cz-(CH ) -[2.2]PCP-(CH ) -NI 1 (blue), Cz-(CH ) -[3.3]PCP-(CH ) -NI 2 (green), Cz-(CH ) -[2.2]PCP-
2
3
2
3
2
3
2
3
2 2
(
CH ) -NI 3 (light blue), PTZ-(CH ) -[2.2]PCP-(CH ) -NI 4 (red), PTZ-(CH ) -[3.3]PCP-(CH ) -NI 5 (purple) in CH CN (λ = 330 nm). (b)
2 2 2 3 2 3 2 3 2 3 3 ex
Fluorescence spectra of Br-(CH ) -[2.2]PCP-(CH ) -NI 11 (blue), Br(CH ) -[3.3]PCP-(CH ) -NI 16 (red), and Br(CH ) -[2.2]PCP-(CH ) -NI 20
2
3
2
3
2
3
2
3
2
2
2 2
(
green) in CH CN (λ = 330 nm).
3 ex
Figure 5. Reference compounds 23−25.
quite similar absorption spectra to each other at 257 nm as a
sharp band and at ca. 280−360 nm as a structured broad band,
which are a superposition of those of the components, Me-PTZ
and Me-NI. Me-PTZ-(CH ) -[2.2]PCP-(CH ) -BTD 6 shows a
bands at 350 and 367 nm, but also a broad band at 441 nm (Φ
f
0.009) in cyclohexane. The latter broad band can be assigned as
the fluorescence band due to the exciplex formation between the
NI and [2.2]PCP moieties since Br(CH ) -[2.2]PCP-(CH ) -
2
2
2 2
2 3
2 3
sharp band at 258 nm and a structured broad band at ca. 310 nm,
and the spectrum is the simple superposition of those of the Me-
PTZ and Me-BTD. These data clearly indicated that the
chromophores (D, D′, A) do not interact with each other in
the ground state, as was supported by the redox potentials. No
significant solvent effect was observed in the absorption spectra
of 1−6 in cyclohexane, CH Cl and CH CN, and no CT band
was observed for any of the evaluated compounds (Figures S4
and S5). Thus, we confirmed that the magnitude of the electronic
interaction among the chromophores can be significantly
reduced in the ground state by connecting the chromophores
with a single oligomethylene chain.
NI 11 also shows a similar broad band at 441 nm (Φ 0.009) in
f
cyclohexane (Figure 3b). The bands in the shorter wavelength
region are assigned as those due to the Cz and NI moieties, but
their intensities are significantly decreased compared to those of
Me-Cz and Me-NI. When the Cz moiety of 1 is selectively excited
at 262 nm in cyclohexane, the fluorescence band appears at 443
nm due to the exciplex formation between the NI and [2.2]PCP
moieties (Figure S10), and the excitation spectrum at 443 nm is
similar to the absorption spectrum of Me-Cz (Figure S11). In
addition, the fluorescence spectrum of Cz-(CH ) -[2.2]PCP-
2
2,
3
2
3
(CH ) Br 23 is quite similar to that of Me-Cz and the quantum
2
3
yield is slightly decreased (λmax = 348 and 364 nm, Φ 0.57) in
f
Fluorescence Spectra. The fluorescence spectra of the D−
D′−A triads 1−5 and their components, Me-NI, Me-Cz, and Me-
PTZ, were measured at 330 nm as the excited wavelength in
diluted cyclohexane (Figures 3a and S7), CH Cl (Figure S8),
cyclohexane (Figure S7c). These results indicated that the Cz
moiety and the [2.2]PCP moiety do not interact with each other
in the excited state and the intramolecular energy transfer from
the Cz moiety in the excited state to the NI moiety is expected in
1. In sharp contrast, the triad 1 shows only a broad structured
fluorescence band at 354 and 369 nm in CH Cl (Figure S8a)
2
2
−5
and CH CN (Figures 4a and S9) solutions (≤10 M) to
3
eliminate the intermolecular interaction. The fluorescence
2
2
spectra of the reference compounds, such as Br(CH ) -
and at 368 nm in CH CN (Figure 4a) (Φ 0.006 in CH Cl , 0.004
2
3
3
f
2
2
[
2.2]PCP-(CH ) -NI 11, Br(CH ) -[3.3]PCP-(CH ) -NI 16,
in CH CN). The exciplex emission is quenched in CH Cl and
2
3
2 3
2 3
3
2
2
and Br(CH ) -[2.2]PCP-(CH ) -NI 20 (Figures 3b, 4b, and
CH CN, suggesting the presence of a photoinduced charge
3
2
2
2 2
•+
•−
Figure S8b), as well as Cz-(CH ) -[2.2]PCP-(CH ) Br 23
separated state, Cz -(CH ) -[2.2]PCP-(CH ) -NI .
2
3
2 3
2 3 2 3
(Figures 5, S7c, S8e, and S9c) were also measured under the
The fluorescence spectra of Cz-(CH ) -[3.3]PCP-(CH ) -NI
2 3 2 3
same conditions. All the data are summarized in Table 3.
2 in cyclohexane and CH CN are similar to those of 1, suggesting
3
Me-NI exhibits structured low intensity fluorescence bands at
the presence of an intramolecular energy transfer from the Cz
moiety in the excited state to the NI moiety in cyclohexane and a
3
49, 366, and 387 nm (Φ 0.005), while Me-Cz shows
f
significantly high intensity fluorescence bands at 345 and 362
nm (Φ 0.68) in cyclohexane (Figure S7a). Cz-(CH ) -
photoinduced charge separation process in CH CN. Interest-
3
ingly, 2 shows a much higher intensity band due to the exciplex
f
2 3
[
2.2]PCP-(CH ) -NI 1 shows not only structured fluorescence
formation at 465 nm (Φ 0.050) in cyclohexane and at 542 nm
2
3
f
F
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Table 3. Fluorescence Data of the Triads 1−5, 11, 16, 20, 23, 6, 24, 25, Me-NI, Me-Cz, Me-PTZ, and Me-BTD in Cyclohexane,
CH Cl , and CH CN
2
2
3
a
λmax/nm (Φ )
f
compound
Cz-(CH ) -[2.2]PCP-(CH ) -NI 1
cyclohexane
CH Cl2
CH CN
3
2
b
b
b
350, 367, 441 (0.009)
348, 365, 465 (0.050)
349, 366 (0.004)
366, 448, 519 (0.008)
459 (0.015)
354, 369, 560 (0.006)
353, 368, 542 (0.012)
354, 368, 544 (0.003)
377, 449 (0.004)
379, 447 (0.004)
362, 379, 504 (0.031)
375, 534 (0.019)
370, 377, 540 (0.004)
352, 369 (0.31)
368 (0.004)
2
3
2 3
Cz-(CH ) -[3.3]PCP-(CH ) -NI 2
353, 368 (0.005)
367 (0.003)
2
3
2 3
Cz-(CH ) -[2.2]PCP-(CH ) -NI 3
2
2
2 2
b
b
PTZ-(CH ) -[2.2]PCP-(CH ) -NI 4
379, 443 (0.005)
364, 446 (0.005)
363, 377, 535 (0.004)
365 (0.004)
2
3
2 3
PTZ-(CH ) -[3.3]PCP-(CH ) -NI 5
2
3
2 3
b
b
b
b
Br(CH ) -[2.2]PCP-(CH ) -NI 11
350, 367, 441 (0.006)
458 (0.051)
2
3
2 3
Br(CH ) -[3.3]PCP-(CH ) -NI 16
2
3
2 3
Br(CH ) -[2.2]PCP-(CH ) -NI 20
349, 368 (0.003)
348, 364 (0.57)
407 (0.012)
364 (0.003)
2
2
2 2
Cz-(CH ) -[3.3]PCP-(CH ) Br 23
352, 368 (0.53)
450 (0.004)
2
3
2 3
c
Me-PTZ-(CH ) -[2.2]PCP-(CH ) -BTD 6
450 (0.004)
2
2
2 2
c
[
2.2]PCP-(CH ) -BTD 24
394 (0.014)
499 (0.006)
537 (0.004)
2
2
c
Me-PTZ-(CH ) -[2.2]PCP 25
445 (0.010)
451 (0.011)
450 (0.011)
2
2
b
Me-NI
Me-Cz
349, 366, 387 (0.005)
345, 362 (0.68)
361, 379 (0.040)
351, 368 (0.34)
361, 377 (0.029)
352, 368 (0.61)
b
b
c
b
c
b
c
Me-PTZ
Me-BTD
442 ; 444 (0.009)
448 ; 449 (0.010)
445 ; 447 (0.011)
c
389 (0.013)
409 (0.022)
414 (0.027)
a
b
c
Absolute quantum yields. λ = 330 nm. λ = 312 nm.
ex
ex
(
Φ 0.012) in CH Cl (Figure S8a) than that of the [2.2]PCP-
because of the limited solubility of [2.2]PCP and Me-NI in
cyclohexane. A more detailed study is required for the
assignment of this band.
f
2
2
based triad 1, and this indicated that the [3.3]PCP moiety has a
stronger tendency to form the exciplex with the NI moiety than
the [2.2]PCP moiety, probably because of the stronger electron
donating ability of the former than the latter (Table 1). The
fluorescence spectrum of Cz-(CH ) -[2.2]PCP-(CH ) -NI 3 is
solvent dependent. In cyclohexane, 3 shows only broad
structured bands at 349 and 366 nm (Φ 0.004) and the band
due to the exciplex emission cannot be observed, similar to the
In CH Cl and CH CN, 4 shows two structured fluorescence
2
2
3
22
bands at 377 and 449 nm (Φ 0.004) in CH Cl as well as at 379
f
2
2
2
2
2 2
and 443 nm (Φ 0.005) in CH CN due to the NI and PTZ
f
3
moieties, respectively, suggesting the presence of a photoinduced
charge separation process in these solvents. PTZ-(CH ) -
f
2
3
[
3.3]PCP-(CH ) -NI 5 also shows a broad fluorescence band
2 3
fluorescence spectrum of Br(CH ) -[2.2]PCP-(CH ) -NI 20 in
cyclohexane, while 3 shows the exciplex band at 499 nm in
2
2
2 2
at 459 nm (Φ 0.015) in cyclohexane, which is assigned as the
f
overlap of the bands due to the PTZ moiety and the exciplex
emission between the NI and [3.3]PCP moieties, but the band
due to the exterplex emission is not observed. The triads 4 and 5
show only broad structured bands due to the NI and PTZ
moieties, respectively, in CH CN (4: 379 and 443 nm, Φ 0.005;
23
toluene (Figure S12). These results clearly indicated that a
trimethylene chain is more favorable as a linker for the formation
of the exciplex than a dimethylene chain, as suggested by a
statistical rule known as Hirayama’s n = 3 rule. Similar to the
cases of 1 and 2, the photoinduced charge separation process is
expected for 3 in CH CN.
As a reference experiment, we examined the intermolecular
exciplex formation between the PCP and NI moieties in
24
3
f
5
: 364 and 446 nm, Φ 0.005), suggesting a photoinduced charge
f
3
separation process.
The fluorescence spectra of Me-PTZ-(CH ) -[2.2]PCP-
2
2
(
CH ) -BTD 6 and its reference compounds, such as Me-
−2
2 2
cyclohexane. In a mixture of [3.3]PCP (10 M) and Me-NI
BTD, Me-PTZ, [2.2]PCP-(CH ) -BTD 24, and Me-PTZ-
−4
2 2
(10 M) in cyclohexane, the intermolecular exciplex band was
(
CH ) -[2.2]PCP 25 were measured in cyclohexane (Figure
2 2
clearly observed, while its intensity at 440−540 nm was
S7d), CH Cl (Figure S8f) and CH CN (Figure S9d) using 312
2
2
3
significantly decreased in the solution of a mixture of [3.3]
−
5
PCP (10−3 M) and Me-NI (10−4 M) (Figure S13). Similar weak
nm light for excitation and a 10 M sample concentration to
eliminate any intermolecular interaction. The triad 6 shows a
broad fluorescence band due to both the BTD and PTZ moieties
band due to the intermolecular exciplex was observed in a
−3
−4
mixture of [2.2]PCP (10 M) and Me-NI (10 M), while the
clear exciplex band was not observed because of the limited
solubility of [2.2]PCP in cyclohexane.
in cyclohexane (Φ 0.012), whereas 6 exhibits a broad and low
f
intensity fluorescence band at 450 nm (Φ 0.004) in CH Cl and
f
2
2
CH CN, and the λ and its intensity are similar to those of Me-
The triad with a different D−A combination, PTZ-(CH ) -
3
max
2
3
PTZ due to the quenching of the fluorescence band by the BTD
moiety. This indicated a photoinduced charge separation
[
2.2]PCP-(CH ) -NI 4, shows two structured fluorescence
2 3
bands at 366 and 448 nm due to the NI and PTZ moieties,
respectively, and a broad band in a much longer wavelength
region (519 nm, Φ 0.008) than that of the exciplex between the
NI and [2.2]PCP moieties in cyclohexane. The band at 519 nm is
associated with the formation of the exterplex (termolecular
exciplex) among the NI, [2.2]PCP, and PTZ moieties because
the excitation spectrum of 4 at 520 nm is a superposition of the
absorption spectra of Me-PTZ and Me-NI in cyclohexane
process. [2.2]PCP-(CH ) -BTD 24 shows a fluorescence band
2 2
similar to Me-BTD in cyclohexane (394 nm, Φ 0.014), whereas
f
f
the exciplex emission between the BTD and [2.2]PCP moieties
is observed in CH Cl (Scheme S8f) and CH CN (Scheme S9d).
2
2
3
2
5
The fluorescence spectrum and its quantum yield of Me-PTZ-
(CH -[2.2]PCP 25 are similar to those of Me-PTZ in
cyclohexane, CH Cl , and CH CN, indicating that the PTZ
)
2 2
2
2
3
(Figure S14). The formation of the intermolecular exterplex
moiety in the excited state cannot interact with the [2.2]PCP
among Me-NI, [2.2]PCP, and Me-PTZ could not be examined
moiety in 25 and 6.
G
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Article
under reduced pressure, and the residue was purified by SiO column
3
. CONCLUSIONS
The new D−D′−A triads with three types of the D−A
combinations, Cz-(CH ) -[n.n]PCP-(CH ) -NI (1: n = 2, m
2
chromatography containing 10 wt % K CO (hexane/CH Cl , 5/1, R =
2
3
2
2
f
0
.27). The eluate was evaporated under reduced pressure and the solid
2
m
2 m
was washed with MeOH to give 4,12-diallyl[2.2]PCP 8 as colorless
1
=
3; 2, n = 3, m = 3; 3, n = 2, m = 2), PTZ-(CH ) -[n.n]PCP-
2 m
powder (1.25 g, 87%): mp 106−108 °C; H NMR (600 MHz, CDCl ) δ
3
(
CH ) -NI (4: n = 2, m = 3; 5: n = 3, m = 3), and Me-PTZ-
2.77 (m, 2H), 3.01 (m, 4H), 3.09 (m, 2H), 3.32 (m, 2H), 3.38 (m, 2H),
2
m
(
CH ) -[2.2]PCP-(CH ) -BTD 6 were successfully synthesized.
5.04 (m, 4 H), 5.85 (m, 2H), 6.13 (s, 1H), 6.31 (d, J = 7.8 Hz, 2H), 6.64
2
2
2 2
(dd, J = 7.8, 1.8 Hz, 2H); 13C NMR (150 MHz, CDCl
) δ 32.8, 33.5,
8.8, 115.6, 126.7, 133.6, 134.3, 136.8, 137.6, 139.2, 139.4; HRMS
The redox potentials of 1−6 in CH CN are in good agreement
3
3
3
(
with those of the donor and acceptor components. The
absorption spectra of 1−6 show spectra similar to a superposition
of those of the components in cyclohexane, CH Cl , and
+
FAB-TOF) m/z calcd. for C H 288.1878 [M ], found 288.1881.
22 24
Anal. Calcd for C H : C, 91.61; H, 8.39. Found: C, 91.42; H, 8.42.
22
24
2
2
4
,12-Bis(3-bromopropyl)[2.2]paracyclophane 10. 4,12-Diallyl-
2.2]PCP 8 (0.29 g, 1.00 mmol) was added to a 0.5 M THF solution of
-BBN (8.0 mL, 4.0 mmol) under an Ar atmosphere, and the mixture
CH CN. No significant solvent effect was observed in the
absorption spectra of 1−6 in cyclohexane, CH Cl and CH CN,
and no CT band was observed for any of the evaluated
compounds. These data clearly indicate that the chromophores
do not interact with each other in the ground state, as we
expected at the start of this study.
3
[
2
2,
3
9
was stirred at 40 °C for 3 h. After cooling to 0 °C, water, 2 M aqueous
NaOH solution (8.0 mL), and then 30% H O (4.0 mL) were added to
2
2
the reaction mixture. The mixture was continuously stirred overnight at
room temperature. Aqueous Na SO solution was added to the reaction
2
3
mixture at 0 °C, and the mixture was extracted with AcOEt/THF = 6/1.
All the fluorescence spectra of 1−6 are quenched in CH CN,
3
The organic layer was dried with Na SO , filtered, the filtrate was
suggesting the presence of a photoinduced charge separation
2
4
concentrated under reduced pressure, and the concentrate was purified
process. In the same D−A combination, Cz-(CH ) -[3.3]-PCP-
2
3
by SiO column chromatography (CH Cl then CH Cl /MeOH, 50/1,
2
2
2
2
2
(
CH ) -NI 2 shows a more intensive exciplex emission band than
2 3
Rf = 0.13) to give 4,12-bis(3-hydroxypropyl)[2.2]PCP 9 as colorless
waxy solid. This compound was used for next reaction without further
purification. HRMS (FAB-TOF) m/z calcd. for C H O 324.2089
in Cz-(CH ) -[2.2]-PCP-(CH ) -NI 1 in cyclohexane, while Cz-
2
3
2 3
(CH ) -[2.2]PCP-(CH ) -NI 3 do not show any exciplex
2 2 2 2
22
28
2
emission in cyclohexane. These results suggest that a
combination of [3.3]PCP as D′ and a trimethylene chain as a
linker is more suitable for the formation of the exciplex than that
of [2.2]PCP and a dimethylene chain, probably because of higher
+
[
M ], found 324.2091.
To the diol 9 in CH Cl (10.0 mL) was added PPh (1.05 g, 4.00
2
2
3
mmol) and then CBr (1.33 g, 4.01 mmol) at 0 °C, and the mixture was
4
stirred at room temperature for 3 h. The reaction mixture was passed
22
through SiO column chromatography with CH Cl and the filtrate was
electron donating ability of [3.3]PCP.
2
2
2
concentrated under reduced pressure. The concentrate was purified by
SiO column chromatography (hexane/CH Cl , 5/1, R = 0.38) to give
In the triads with the PTZ (D) and NI (A) combination, PTZ-
2
2
2
f
(CH ) -[2.2]PCP-(CH ) -NI 4 show a broad fluorescence band
2
3
2 3
4
,12-bis(3-bromopropyl)[2.2]PCP 10 as colorless powder (0.43 g, 96%
at 519 nm in cyclohexane, which may be associated with the
exterplex among the NI, [2.2]PCP, and PTZ moieties, while
PTZ-(CH ) -[3.3]PCP-(CH ) -NI 5 does not show this type of
band, but shows a broad fluorescence band, which may be
assigned as the superposition of the bands due to the exciplex
formation between the NI and PCP moieties and the PTZ
moiety in cyclohexane. The triads 4 and 5 show only broad
1
from 8): mp 124−126 °C; H NMR (600 MHz, CDCl ) δ 1.99 (quint., J
=
3
7.2 Hz, 4H), 2.44 (m, 2H), 2.78 (m, 4H), 3.02 (m, 4H), 3.33 (m, 6H),
2
3
2 3
6.13 (d, J = 1.2 Hz, 2H), 6.34 (d, J = 7.8 Hz, 2H), 6.62 (dd, J = 7.8, 1.2
Hz, 2H); 13C NMR (150 MHz, CDCl ) δ 32.7, 33.0, 33.4, 33.6, 33.7,
3
127.1, 133.8, 134.9, 137.4, 139.5, 140.2; HRMS (FAB-TOF) m/z calcd.
+
for C H Br 448.0401 [M ], found 448.0403. Anal. Calcd for
2
2
26
2
C
H
4
26Br
: C, 58.69; H, 5.82. Found: C, 58.73; H, 5.84.
-(3-Bromopropyl)-12-[3-{N-(1,8-naphthalimidyl)}propyl]-
2.2]paracyclophane 11. A mixture of 1,8-naphthalimide (98.9 mg,
.50 mmol), Cs CO (0.33 mg, 1.01 mmol), and DMF (10 mL) was
22
2
structured bands due to the NI and PTZ moieties in CH CN,
suggesting a photoinduced charge separation process. Me-PTZ-
3
[
0
2
3
(
CH ) -[2.2]PCP-(CH ) -BTD 6 shows a broad fluorescence
2 2 2 2
stirred at room temperature for 20 min. To the mixture was added 4,12-
bis(3-bromopropyl)[2.2]PCP 10 (225 mg, 0.50 mmol), and the mixture
was stirred overnight at room temperature. The reaction mixture was
band due to both the BTD and PTZ moieties in cyclohexane,
whereas 6 exhibits a broad and low intensity fluorescence band
due to the PTZ moiety in CH Cl and CH CN, indicating a
photoinduced charge separation process.
2
2
3
extracted with CH
Cl , and the combined CH Cl extract was dried with
2 2 2 2
Na SO , filtered, and the filtrate was concentrated under reduced
2
4
Thus, the electronic interaction between the PCP and
acceptor moieties can be observed as the exciplex formation in
cyclohexane. The formation of the exciplex is more significant in
the triad with a [3.3]PCP moiety as D′ and a trimethylene chain
as a linker. In all the triads 1−6, the quenching of the
pressure. The concentrate was purified by SiO
(hexane/CH Cl , 1/2, R = 0.28) to give 4-(3-bromopropyl)-12-[3-{N-
1,8-naphthalimidyl)}-propyl][2.2]PCP 11 as colorless powder (0.14 g,
2
column chromatography
2
2
f
(
−1 1
4
8%): mp 202−204 °C; IR (Nujol) ν 1660, 1699 (CO) cm ; H
NMR (600 MHz, CDCl ) δ 1.91 (quint., J = 7.8 Hz, 2H), 1.98 (quint., J
3
=
7.2 Hz, 2H), 2.44 (m, 2H), 2.76 (m, 4H), 2.98 (m, 4H), 3.33 (m, 4H),
fluorescence band is observed in CH CN, which suggests the
3
4
6
.22 (t, J = 7.8 Hz, 2H), 6.10 (d, J = 1.2 Hz, 1H), 6.16 (d, J = 1.2 Hz, 1H),
.27 (d, J = 7.8 Hz, 1H), 6.32 (d, J = 7.8 Hz, 1H), 6.53 (dd, J = 7.8, 1.8
presence of the charge separated state, probably starting from D-
•
+
(
(
CH ) -[n.n]PCP-(CH ) -A* to D -(CH ) -[n.n]PCP-
2 m 2 m 2 m
Hz, 1H), 6.61 (dd, J = 7.8, 1.2 Hz, 1H), 7.75 (t, J = 7.8 Hz, 2H), 8.21 (d, J
•
−
•+
•−
13
CH ) -A via D-(CH ) -[n.n]PCP -(CH ) -A . Our col-
= 7.8 Hz, 2H), 8.59 (d, J = 7.8 Hz, 2H); C NMR (150 MHz, CDCl ) δ
2
m
2 m
2 m
3
laborators have studied the photoinduced charge separation
processes of the triads 1−6 and the reference compounds in
detail using the transient absorption spectra, the result of which
will be soon reported elsewhere. Syntheses of the next triads with
triple-layered [2.2]- and [3.3]PCPs are also in progress.
28.6, 32.1, 32.7, 33.0, 33.5, 33.6, 33.7, 33.8, 40.6, 122.8, 126.8, 126.9,
128.2, 131.2, 131.6, 133.7, 133.9, 134.3, 134.9, 137.2, 137.4, 139.2, 139.5,
1
5
7
40.1, 141.0, 164.2; HRMS (FAB-TOF) m/z calcd. for C H BrNO
34 32 2
+
65.1616 [M ], found 565.1628. Anal. Calcd for C H BrNO : C,
34 32
2
2.08; H, 5.69; N, 2.47. Found: C, 72.26; H, 5.76; N, 2.44.
4
-{3-(N-Carbazolyl)propyl}-12-[3-{N-(1,8-naphthalimidyl)}-
propyl][2.2]paracyclophane 1. A mixture of 4-(3-bromopropyl)-12-
3-{N-(1,8-naphthalimidyl)}propyl][2.2]PCP 11 (167 mg, 0.29
4
. EXPERIMENTAL SECTION
[
4
,12-Diallyl[2.2]paracyclophane 8. A mixture of 4,12-
mmol), carbazole (60.0 mg, 0.36 mmol), n-Bu NBr (48.2 mg, 0.15
4
dibromo[2.2]PCP 7 (1.83 g, 5.00 mmol), allyltributyltin (7.28 g, 22.0
mmol), toluene (6 mL), and a 2 M aqueous NaOH solution (6 mL) was
refluxed for 2 d. The reaction mixture was extracted with toluene, the
combined toluene extract was dried, filtered, and the filtrate was
mmol), Pd(PPh ) (0.92 g, 0.80 mmol), and DMF (180 mL) was stirred
3
4
at 100 °C for 36 h under an Ar atmosphere. The solvent was removed
H
dx.doi.org/10.1021/jo5020273 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
−
1 1
concentrated under reduced pressure. The concentrate was purified by
SiO column chromatography (hexane/CH Cl , 1/3, R = 0.35) to give
145 °C; IR (Nujol) ν 1661, 1670 (CO) cm ; H NMR (600 MHz,
CDCl ) δ 2.02 (m, 8H), 2.60 (m, 8H), 2.91 (m, 4H), 3.37 (m, 2H), 4.27
2
2
2
f
3
4
-{3-(N-carbazolyl)propyl}-12-[3-{N-(1,8-naphthalimidyl)}propyl]-
(t, J = 7.8 Hz, 2H), 6.40 (d, J = 7.2 Hz, 1H), 6.45 (d, J = 7.8 Hz, 1H), 6.51
[
(
1
2
2.2]PCP 1 as yellow powder (186 mg, quant.): mp 100−101 °C; IR
(m, 2H), 6.56 (s, 1H), 6.63 (s, 1H), 7.76 (t, J = 7.8 Hz, 2H), 8.21 (d, J =
−1
1
13
Nujol) ν 1659, 1699 (CO) cm ; H NMR (600 MHz, CDCl ) δ
8.4 Hz, 2H), 8.61 (d, J = 7.8 Hz, 2H); C NMR (150 MHz, CDCl ) δ
3
3
.89 (m, 2H), 2.04 (m, 2H), 2.33 (m, 1H), 2.43 (m, 1H), 2.73 (m, 5H),
.87 (m, 1H), 3.00 (m, 3H), 3.34 (m, 1H), 4.22 (m, 4H), 6.07 (d, J = 1.2
28.5, 28.7, 30.7, 31.5, 32.2, 33.7, 33.8, 35.4, 40.6, 122.8, 125.7, 126.0,
126.9, 128.2, 129.4, 129.9, 131.2, 131.6, 133.8, 135.6, 135.8, 137.0, 137.9,
138.7, 138.9, 164.2; HRMS (FAB-TOF) m/z calcd. for C H BrNO
2
Hz, 1H), 6.10 (d, J = 1.2 Hz, 1H), 6.16 (d, J = 7.2 Hz, 1H), 6.30 (d, J =
7
7
3
6
36
+
.2 Hz, 1H), 6.31 (dd, J = 7.2, 1.8 Hz, 1H), 6.61 (dd, J = 7.8, 1.8 Hz, 1H),
.22 (t, J = 7.2 Hz, 2H), 7.30 (d, J = 8.4 Hz, 2H), 7.44 (m, 2H), 7.74 (dd,
593.1929 [M ], found 593.1929. Anal. Calcd for C H BrNO : C,
36 36 2
72.72; H, 6.10; N, 2.36. Found: C, 72.57; H, 6.13; N, 2.26.
J = 8.4, 7.8 Hz, 2H), 8.10 (d, J = 7.2 Hz, 2H), 8.20 (dd, J = 7.8, 1.2 Hz,
4-{3-(N-Carbazolyl)propyl}-16-[3-{N-(1,8-naphthalimidyl)}-
propyl][3.3]paracyclophane 2. This compound was synthesized by
the similar procedures to those of 1 (79%). Yellow powder: mp 80−82
2
2
1
1
1
H), 8.59 (dd, J = 7.8, 1.2 Hz, 2H); 13C NMR (150 MHz, CDCl ) δ
3
8.6, 29.2, 31.8, 32.0, 32.9, 32.9, 33.4, 33.5, 40.5, 42.5, 108.7, 118.8,
20.3, 122.7, 122.9, 125.6, 126.3, 126.8, 126.9, 128.2, 131.2, 131.6, 133.5,
33.8, 133.9, 134.2, 134.3, 137.1, 137.4, 139.1, 137.4, 140.4, 140.9,
−1 1
°C; IR (Nujol) ν 1660, 1699 (CO) cm ; H NMR (600 MHz,
CDCl ) δ 1.94 (m, 5H), 2.09 (m, 3H), 2.45 (m, 2H), 2.58 (m, 7H), 2.87
3
+
64.1; HRMS (FAB-TOF) m/z calcd. for C H N O 652.3090 [M ],
(m, 3H), 4.27 (quint. J = 7.8 Hz, 4H), 6.27 (d, J = 8.4 Hz, 1H), 6.38 (d, J
= 7.8 Hz, 1H), 6.49 (m, 2H), 6.53 (s, 1H), 6.59 (s, 1H), 7.22 (t, J = 7.8
Hz, 2H), 7.32 (d, J = 8.4 Hz, 2H), 7.44 (t, J = 7.8 Hz, 2H), 7.75 (t, J = 7.8
Hz, 2H), 8.10 (d, J = 7.8 Hz, 2H), 8.21 (d, J = 8.4 Hz, 2H), 8.60 (d, J =
46
40
2
2
found 652.3093. Anal. Calcd for C H N O : C, 84.63; H, 6.18; N, 4.29.
46
40
2
2
Found: C, 84.62; H, 6.47; N, 4.22.
-[3-{N-(1,8-Naphthalimidyl)}propyl]-12-[3-{N-(10H-pheno-
4
13
thiazinyl)}propyl][2.2]paracyclophane 4. A mixture of 10H-
phenothiazine (12.4 mg, 0.06 mmol), t-BuOK (8.1 mg, 0.07 mmol)
and DMF (1.0 mL) was stirred at room temperature for 10 min under an
Ar atmosphere. To the mixture was added 4-(3-bromopropyl)-12-[3-
7.2 Hz, 2H); C NMR (150 MHz, CDCl ) δ 28.3, 28.7, 29.4, 30.5, 30.7,
3
32.2, 35.3, 35.4, 40.6, 42.6, 108.7, 118.7, 120.3, 122.7, 122.9, 125.5,
125.6, 125.9, 126.9, 128.2, 129.4, 131.2, 131.6, 133.9, 135.6, 135.8, 137.4,
137.9, 138.6, 138.8, 140.4, 164.2; HRMS (FAB-TOF) m/z calcd. for
+
{N-(1,8-naphthalimidyl)}-propyl][2.2]PCP 11 (28.6 mg, 0.05 mmol),
C H N O 680.3403 [M ], found 680.3403. Anal. Calcd for
4
8
44
2
2
and the mixture was stirred overnight under an Ar atmosphere. The
reaction mixture was extracted with CH Cl , and the combined CH Cl
2
C H N O : C, 84.67; H, 6.51; N, 4.11. Found: C, 84.33; H, 6.78; N,
3.93.
48 44 2 2
2
2
2
extract was dried with Na SO , filtered, and the filtrate was concentrated
4-[3-{N-(1,8-Naphthalimidyl)}propyl]-16-[3-{N-(10H-pheno-
thiazinyl)}propyl][3.3]paracyclophane 5. This compound was
synthesized by the similar procedures to those of 4 (59%). Yellow
2
4
under reduced pressure. The concentrate was purified by SiO column
2
chromatography (hexane/CH Cl , 1/2, R = 0.45) to give 4-[3-{N-(1,8-
2
2
f
−1 1
naphthalimidyl)}propyl]-12-[3-{N-(10H-phenothiazinyl)}propyl]-
powder: mp 229−231 °C; IR (Nujol) ν 1660, 1699 (CO) cm ; H
[
°
2.2]paracyclophane 4 as yellow powder (9.6 mg, 28%): mp 198−199
NMR (600 MHz, CDCl ) δ 1.96 (m, 9H), 2.35 (m, 1H), 2.58 (m, 9H),
3
−1 1
C; IR (Nujol) ν 1654, 1699 (CO) cm ; H NMR (600 MHz,
2.89 (m, 3H), 3.83 (m, 2H), 4.25 (t, J = 7.8 Hz, 2H), 6.31 (d, J = 7.2 Hz,
1H), 6.37 (d, J = 7.8 Hz, 1H), 6.46 (m, 3H), 6.58 (s, 1H), 6.80 (d, J = 7.8
Hz, 2H), 6.91 (t, J = 7.8 Hz, 2H), 7.11 (t, J = 7.2 Hz, 2H), 7.17 (d, J = 7.8
Hz, 2H), 7.75 (t, J = 7.8 Hz, 2H), 8.21 (d, J = 8.4 Hz, 2H), 8.60 (d, J = 7.2
CDCl ) δ 1.91 (m, 4H), 2.39 (m, 2H), 2.56 (m, 1H), 2.72 (m, 3H), 2.90
3
(
m, 4H), 3.04 (m, 1H), 3.32 (m, 1H), 3.82 (br, 2H), 4.20 (t, J = 7.8 Hz,
H), 6.00 (s, 1H), 6.09 (s, 1H), 6.15 (d, J = 7.8 Hz, 1H), 6.24 (d, J = 7.8
Hz, 1H), 6.40 (d, J = 7.8 Hz, 1H), 6.56 (d, J = 7.8 Hz, 1H), 6.79 (d, J =
2
Hz, 2H); 13C NMR (150 MHz, CDCl
) δ 27.5, 28.6, 28.7, 30.0, 30.7,
3
7
2
2
4
1
1
.8 Hz, 2H), 6.92 (br, 2H), 7.12 (t, J = 7.8 Hz, 2H), 7.18 (d, J = 7.8 Hz,
35.3, 40.6, 46.5, 115.8, 122.4, 133.8, 125.6, 125.7, 126.9, 127.1, 127.4,
128.2, 129.3, 130.1, 131.2, 131.6, 133.8, 135.6, 135.8, 137.8, 137.9, 138.6,
H), 7.74 (t, J = 7.8 Hz, 2H), 8.20 (d, J = 7.8 Hz, 2H), 8.59 (d, J = 7.8 Hz,
H); 13C NMR (150 MHz, CDCl ) δ 28.6, 31.2, 32.0, 32.7, 33.0, 33.5,
138.7, 145.3, 164.2; HRMS (FAB-TOF) m/z calcd. for C48H N O S
3
44 2 2
+
0.5, 115.8, 122.5, 122.7, 126.6, 126.7, 126.9, 127.2, 127.5, 128.2, 131.2,
31.6, 133.5, 133.8, 134.2, 134.6, 137.0, 137.5, 139.3, 140.8, 140.9,
712.3123 [M ], found 712.3109. Anal. Calcd for C48
80.86; H, 6.22; N, 3.93. Found: C, 80.74; H, 6.32; N, 3.79.
4,12-Divinyl[2.2]paracyclophane 17. This compound was
H N O S: C,
44 2 2
+
64.1; HRMS (FAB-TOF) m/z calcd. for C H N O S 684.2810 [M ],
46
40
2
2
2
6
found 684.2812. Anal. Calcd for C H N O S: C, 80.67; H, 5.89; N,
4
synthesized according to the reported procedures. A mixture of
46
40
2
2
.09. Found: C, 80.59; H, 6.13; N, 3.92.
,16-Diallyl[3.3]paracyclophane 13. 4,16-Diallyl[3.3]-
4,12-dibromo[2.2]PCP 7 (1.10 g, 3.00 mmol), vinyltributyltin (5.76 g,
4
18.2 mmol), Pd(PPh
stirred at 100 °C for 1 d under an Ar atmosphere. The reaction mixture
was passed through a silica gel containing 10 wt % K CO with toluene
3 4
) (0.52 g, 0.45 mmol), and toluene (120 mL) was
paracyclophane 13 was synthesized by the similar procedures as
described for 8 (93%). Colorless powder: mp 88−90 °C; H NMR (600
MHz, CDCl ) δ 1.98 (m, 2H), 2.11 (m, 2H), 2.54 (m, 2H), 2.68 (s, 4H),
1
2
3
to remove tin halides, and the eluate was concentrated under reduced
pressure. The concentrate was purified by silica gel column
3
2
.92 (m, 2H), 3.29 (dd, J = 15.6, 6.6 Hz, 2H), 3.51 (dd, J = 15.6, 6.0 Hz,
13
2
H), 5.07 (m, 4H), 5.94 (m, 2H), 6.52 (m, 4H), 6.60 (s, 2H); C NMR
chromatography (hexane/CH
divinyl[2.2]PCP 17 as colorless powder (0.43 g, 56%): H NMR (600
MHz, CDCl ) δ 2.83 (m, 2H), 2.96 (m, 2H), 3.05 (m, 2H), 3.47 (m,
2 2 f
Cl , 5/1, R = 0.33) to give 4,12-
1
(
150 MHz, CDCl ) δ 28.2, 32.4, 35.4, 37.6, 115.4, 125.9, 129.8, 131.4,
3
1
3
8
36.0, 136.3, 137.6, 138.8; HRMS (FAB-TOF) m/z calcd. for C H
3
24
28
+
16.2191 [M ], found 316.2193. Anal. Calcd for C H : C, 91.08; H,
2H), 5.28 (d, J = 10.8 Hz, 2H), 5.52 (d, J = 17.4 Hz), 6.33 (d, J = 7.2 Hz,
24
28
.92. Found: C, 90.77; H, 8.90.
,12-Bis(3-hydroxypropyl)[3.3]PCP 14. This compound was
2H), 6.55 (s, 2H), 6.65 (d, J = 7 0.8 Hz, 2H), 6.82 (dd, J = 17.4, 10.8 Hz,
2
7
13
4
2H) (lit. δ 2.81, 2.94, 3.03, 3.45, 5.27, 5.51, 6.31, 6.54, 6.65, 6.80.);
C
synthesized by the similar procedures to those of 9, and this compound
was used for next reaction without further purification. HRMS (FAB-
TOF) m/z calcd. for C H O 352.2402 [M ], found 352.2403.
NMR (150 MHz, CDCl ) δ 33.0, 34.2, 114.3, 129.3, 130.1, 133.4, 135.3,
3
+
137.7, 139.4; HRMS(FAB-TOF) m/z calcd. for C20H20 260.1565 [M ],
+
found 260.1562.
24
32
2
4
,16-Bis(3-bromopropyl)[3.3]paracyclophane 15. This com-
4,12-Bis(2-bromoethyl)[2.2]paracyclophane 19. 4,12-Divinyl-
[2.2]PCP 17 (0.26 g, 1.00 mmol) was dissolved in a 0.5 M THF solution
of 9-BBN (6.0 mL, 3.0 mmol) under an Ar atmosphere. The mixture was
stirred at 60 °C overnight. After cooling to 0 °C, water, a 2 M aqueous
pound was synthesized from the diol 9 by the similar procedures to
those of 10 (92% from 13). Colorless powder: mp 147−148 °C; H
NMR (600 MHz, CDCl ) δ 2.06 (m, 8H), 2.64 (m, 8H), 2.93 (m, 4H),
1
3
3
2
1
.38 (m, 4H), 6.50 (d, J = 7.8 Hz, 2H), 6.53 (d, J = 7.8 Hz, 2H), 6.58 (s,
NaOH solution (8.0 mL), and aqueous H
successively added to the reaction mixture, and the mixture was
continuously stirred at room temperature for 6 h. Aqueous Na SO
3
2 2
O (4.0 mL) were
H); 13C NMR (150 MHz, CDCl ) δ 28.5, 31.4, 32.3, 33.6, 33.8, 35.4,
3
26.1, 130.0, 131.4, 135.8, 137.2, 138.9; HRMS (FAB-TOF) m/z calcd.
for C H Br 476.0714 [M ], found 476.0738. Anal. Calcd for
2
+
solution was added to the reaction mixture at 0 °C and the mixture was
extracted with AcOEt/THF = 6/1. The combined AcOEt/THF extract
24
30
2
C H Br : C, 60.27; H, 6.32. Found: C, 60.17; H, 6.37.
2
4
4
30
2
-(3-Bromopropyl)-16-[3-{N-(1,8-naphthalimidyl)}propyl]-
was dried with Na SO , filtered, and the filtrate was concentrated under
2 4
[
3.3]paracyclophane 16. This compound was synthesized by the
reduced pressure to give crude 4,12-bis(2-hydroxyethyl)[2.2]PCP 18,
which was used for the next reaction without further purification. HRMS
similar procedures to those of 11 (43%). Pale yellow powder: mp 143−
I
dx.doi.org/10.1021/jo5020273 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
+
(
2
FAB-TOF) m/z calcd. for C H O 297.1855 [M + H ], found
for 2 d under an Ar atmosphere. The reaction mixture was filtered
through a Celite pad, and the filtrate was extracted with AcOEt. The
combined AcOEt extract was dried with Na SO , filtered, and the filtrate
20
25
2
97.1859.
To the diol 18 in CH Cl (10 mL) were added PPh (1.05 g, 4.00
2
2
3
2
4
mmol) and CBr (1.34 g, 4.04 mmol) at 0 °C, and the mixture was
was concentrated under reduced pressure. The concentrate was purified
by silica gel column chromatography (hexane/CH Cl , 2/1, R = 0.13).
4
stirred at room temperature for 1.5 h. Since the TLC (SiO ) analysis of
2
2
2
f
the reaction mixture indicated the presence of the starting compounds,
The eluate was concentrated under reduced pressure, and the
concentrate was washed with MeOH to give 4-[(E)-2-{4-(2,1,3-
benzothiadiazolyl)}vinyl]-12-vinyl[2.2]PCP 21 as yellow powder
additional amounts of PPh (1.05 g, 4.00 mmol) and CBr (1.34 g, 4.04
3
4
mmol) were added and the mixture was stirred at the same temperature
for an additional 1.5 h. Then the reaction mixture was passed through a
SiO column with CH Cl , and the eluate was concentrated under
(0.16 g, 39%). Yellow powder (toluene and MeOH): mp 185−188
1
°C; H NMR (600 MHz, CDCl ) δ 2.96 (m, 3H), 3.11 (m, 3H), 3.51
2
2
2
3
reduced pressure. The concentrate was purified by SiO2 column
(m, 1H), 3.72 (m, 1H), 5.31 (dd, J = 10.8, 1.2 Hz, 1H), 5.55 (dd, J = 17.4,
1.2 Hz, 1H), 6.42 (d, J = 7.8 Hz, 2H), 6.60 (d, J = 1.8 Hz, 1H), 6.72 (td, J
= 7.8, 1.8 Hz, 2H), 6.84 (m, 2H), 7.36 (d, J = 16.2 Hz, 1H), 7.64 (dd, J =
8.4, 7.2 Hz, 1H), 7.69 (d, J = 6.6 Hz), 7.92 (dd, J = 8.4, 0.6 Hz, 1H), 8.23
chromatography (hexane/CH Cl , 5/1, R = 0.30) to give 4,12-bis(2-
2
2
f
bromoethyl)[2.2]PCP 19 as colorless powder (0.38 g, 85% from 17):
1
mp 201−202 °C; H NMR (600 MHz, CDCl ) δ 2.83 (m, 4H), 3.05 (m,
3
(d, J = 16.2 Hz, 1H); 13C NMR (150 MHz, CDCl ) δ 33.0, 33.5, 34.3,
4
H), 3.16 (m, 2H), 3.33 (m, 4H), 3.39 (m, 2H), 6.16 (d, J = 1.8 Hz, 2H),
3
6
.38 (d, J = 7.8 Hz, 2H), 6.64 (dd, J = 7.8, 1.8 Hz, 2H); 13C NMR (150
34.4, 114.4, 119.9, 124.9, 126.6, 129.7, 129.8, 130.2, 130.3, 131.4, 132.7,
133.4, 133.7, 135.3, 137.5, 137.8, 139.0, 139.4, 139.7, 153.4, 155.8;
MHz, CDCl ) δ 32.1, 32.7, 33.5, 38.5, 127.9, 134.0, 135.2, 137.4, 138.6,
3
+
+
1
39.6; HRMS (FAB-TOF) m/z calcd. for C H Br 420.0088 [M ],
HRMS (FAB-TOF) m/z calcd. for C H N S 394.1504 [M ], found
20
22
2
26 22
2
found 420.0094. Anal. Calcd for C H Br : C, 56.90; H, 5.25. Found: C,
394.1494. Anal. Calcd for C H N S: C, 79.15; H, 5.62; N, 7.10. Found:
20
22
2
26 22 2
5
7.13; H, 5.12.
C, 78.94; H, 5.69; N, 6.99.
4
-(2-Bromoethyl)-12-[2-{N-(1,8-naphthalimidyl)}ethyl][2.2]-
4-[(E)-2-{4-(2,1,3-Benzothiadiazolyl)}vinyl]-12-[(E)-2-{3-(10-
methyl-10H-phenothiazinlyl)}vinyl][2.2]paracyclophane 22. A
mixture of 4-[(E)-2-{4-(2,1,3-benzothiadiazolyl)}vinyl]-12-vinyl[2.2]-
PCP 21 (39.4 mg, 0.10 mmol), 3-bromo-10-methyl-10H-phenothiazine
paracyclophane 20. A mixture of 1,8-naphthalimide (39.3 mg, 0.20
mmol), Cs CO (130 mg, 0.40 mmol), and DMF (4 mL) was stirred at
2
3
room temperature for 10 min. To the mixture was added the dibromide
9 (84.5 mg, 0.20 mmol), and the mixture was stirred overnight. The
reaction mixture was extracted with CH Cl , and the combined CH Cl
2
1
(35.4 mg, 0.12 mmol), Pd(dppf)Cl ·CH
CO (69.4 mg, 0.50 mmol), n-Bu NBr (32.1 mg, 0.10 mmol), and
4
2
Cl (4.1 mg, 0.005 mmol),
2 2
K
2
2
2
2
3
extract was dried with Na SO , filtered, and the filtrate was concentrated
DMF (10 mL) was stirred at 100 °C for 1d under an Ar atmosphere. The
reaction mixture was filtered through a Celite pad, and the filtrate was
extracted with AcOEt. The combined AcOEt extract was dried with
2
4
under reduced pressure. The concentrate was purified by SiO column
2
chromatography (hexane/CH Cl , 1/2, R = 0.31) to give 4-(2-
2
2
f
bromoethyl)-12-[2-{N-(1,8-naphthalimidyl)}ethyl][2.2]PCP 20 as
Na
pressure. The concentrate was purified by silica gel column
chromatography (hexane/CH Cl , 3/2, R = 0.39). The eluate was
concentrated under reduced pressure, and the concentrate was washed
with MeOH to give 4-[(E)-2-{4-(2,1,3-benzothiadiazolyl)}vinyl]-12-
[(E)-2-{3-(10-methyl-10H-phenothiazinlyl)}vinyl][2.2]PCP 22 as yel-
2 4
SO , filtered, and the filtrate was concentrated under reduced
colorless powder (49.2 mg, 46%): mp 242−244 °C; IR (Nujol) ν
−
1 1
1
1
1
6
=
655, 1670 (CO) cm ; H NMR (600 MHz, CDCl ) δ 2.71 (m,
2
2
f
3
H), 2.86 (m, 3H), 3.08 (m, 6H), 3.32 (m, 2H), 3.38 (m, 1H), 3.71 (m,
H), 4.20 (m, 2H), 6.15 (s, 1H), 6.34 (s, 1H), 6.36 (d, J = 7.8 Hz, 1H),
.39 (d, J = 7.8 Hz, 1H), 6.62 (m, 2H), 7.79 (t, J = 7.8 Hz, 1H), 8.25 (d, J
13
7.8 Hz, 1H), 8.65 (d, J = 7.8 Hz, 1H); C NMR (150 MHz, CDCl ) δ
low powder (35.9 mg, 59%). Yellow powder (toluene and MeOH): mp
3
1
3
1
1
5
7
2.1, 32.9, 33.3, 33.7, 38.7, 41.1, 122.8, 127.0, 127.6, 128.0, 128.3, 131.3,
31.7, 133.9, 134.0, 134.2, 135.1, 135.6, 137.4, 138.1, 138.4, 138.6, 139.4,
40.0, 164.2; HRMS (FAB-TOF) m/z calcd. for C H BrNO
2
238−239 °C; H NMR (600 MHz, CDCl
3
) δ 2.98 (m, 3H), 3.14 (m,
3H), 3.42 (s, 3H), 3.61 (m, 1H), 3.73 (m, 1H), 6.44 (d, J = 1.2 Hz, 1H),
6.45 (d, J = 1.2 Hz, 1H), 6.67 (d, J = 1.2 Hz, 1H), 6.69 (m, 2H), 6.78 (d, J
= 16.2 Hz, 1H), 6.82 (d, J = 1.2 Hz, 1H), 6.84 (m, 2H), 6.96 (td, J = 7.2,
1.2 Hz, 1H), 7.09 (d, J = 16.2 Hz, 1H), 7.20 (m, 2H), 7.36 (m, 2H), 7.41
(d, J = 1.8 Hz, 1H), 7.64 (dd, J = 8.4, 6.6 Hz, 1H), 7.69 (d, J = 6.6 Hz,
3
2
28
+
37.1303 [M ], found 537.1333. Anal. Calcd for C H BrNO : C,
32
28
2
1.38; H, 5.24; N, 2.60. Found: C, 71.21; H, 5.26; N, 2.63.
-{2-(N-Carbazolyl)ethyl}-12-[2-{N-(1,8-naphthalimidyl)}-
ethyl][2.2]paracyclophane 3. A mixture of the bromide 20 (51.6 mg,
.10 mmol), carbazole (20.1 mg, 0.12 mmol), n-Bu NBr (16.6 mg, 0.051
4
1
3
1H), 7.93 (dd, J = 8.4, 0.6 Hz, 1H), 8.25 (d, J = 16.2 Hz, 1H); C NMR
0
(150 MHz, CDCl ) δ 33.4, 33.5, 34.5, 35.4, 114.1, 119.9, 122.6, 123.0,
4
3
mmol), toluene (2 mL), and a 2 M aqueous NaOH solution. (2 mL) was
refluxed for 2 d. The reaction mixture was extracted with toluene, the
combined toluene extract was dried, filtered, and the filtrate was
concentrated under reduced pressure. The concentrate was purified by
SiO2 column chromatography (hexane/CH Cl , 1/3, R = 0.53),
123.8, 124.5, 124.9, 125.5, 126.2, 126.7, 127.2, 127.5, 128.1, 129.5, 129.7,
130.0, 130.4, 131.4, 132.6, 132.7, 133.6, 137.5, 138.0, 139.0, 139.5, 139.6,
145.2, 145.5, 153.4, 155.8; HRMS (FAB-TOF) m/z calcd. for
+
C H N S 605.1959 [M ], found 605.1957. Anal. Calcd for
3
9
31
3 2
2
2
f
C H N S : C, 77.32; H, 5.16; N, 6.94. Found: C, 77.12; H, 5.07; N,
39 31
3 2
followed by recycling preparative HPLC (GPC, JAIGEL 1H+2H,
6.88.
CHCl ) to give 4-{2-(N-carbazolyl)ethyl}-12-[2-{N-(1,8-
4-[2-{4-(2,1,3-Benzothiadiazolyl)}ethyl]-12-[2-{3-(10-methyl-
10H-phenothiazinlyl)}ethyl][2.2]paracyclophane 6. A mixture of
4-[(E)-2-{4-(2,1,3-benzothiadiazolyl)}vinyl]-12-[(E)-2-{3-(10-methyl-
10H-phenothiazinlyl)}vinyl][2.2]PCP 22 (61.3 mg, 0.10 mmol), 80%
hydrazine monohydrate (0.62 mL, 10.0 mmol), and diethylene glycol
(65 mL) was stirred at 100 °C for 20 h. After cooling to room
temperature, the reaction mixture was extracted with AcOEt. The
3
naphthalimidyl)}ethyl][2.2]PCP 3 as yellow powder (29.0 mg, 48%):
−1 1
mp 233−234 °C; IR (Nujol) ν 1654, 1670 (CO) cm ; H NMR
(
600 MHz, CD Cl ) δ 2.69 (m, 1H), 2.80 (m, 3H), 3.03 (m, 7H), 3.36
2 2
(
t, J = 7.2 Hz, 1H), 3.66 (t, J = 7.2 Hz, 1H), 4.15 (m, 2H), 4.33 (m, 2H),
6
.23 (s, 1H), 6.29 (s, 1H), 6.36 (m, 2H), 6.52 (d, J = 7.2 Hz, 1H), 6.62
(
(
(
d, J = 7.2 Hz, 1H), 7.23 (t, J = 7.8 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.46
t, J = 7.8 Hz, 2H), 7.80 (t, J = 7.8 Hz, 2H), 8.10 (d, J = 7.8 Hz, 2H), 8.27
combined AcOEt extract was dried with Na
was concentrated under reduced pressure. The residue was purified by
silica gel column chromatography (hexane/CH Cl , 1/1, R = 0.39) and
GPC with CHCl to give 4-[2-{4-(2,1,3-benzothiadiazolyl)}ethyl]-12-
2
SO , filtered, and the filtrate
4
13
d, J = 7.8 Hz, 2H), 8.61 (d, J = 7.2 Hz, 2H); C NMR (150 MHz,
CD Cl ) δ 31.0, 33.2, 33.4, 33.6, 34.0, 34.4, 41.3, 44.3, 109.0, 119.2,
2
2
f
2
2
1
20.7, 123.2, 123.3, 126.1, 127.4, 127.9, 128.1, 131.4, 132.2, 134.3, 134.4,
3
1
34.5, 135.8, 138.0, 138.5, 138.7, 138.9, 139.9, 140.4, 140.6, 164.4;
[2-{3-(10-methyl-10H-phenothiazinlyl)}ethyl][2.2]PCP 6 as yellow
+
HRMS (FAB-TOF) m/z calcd. for C H N O 624.2777 [M ], found
powder (25.2 mg, 41%). Yellow powder (toluene and MeOH): mp
44
36
2
2
1
6
24.2780. Anal. Calcd for C H N O : C, 84.59; H, 5.81; N, 4.48.
116−118 °C; H NMR (600 MHz, CDCl
3
) δ 2.52 (m, 1H), 2.61 (m,
44
36
2
2
Found: C, 84.41; H, 5.77; N, 4.46.
-[(E)-2-{4-(2,1,3-Benzothiadiazolyl)}vinyl]-12-vinyl[2.2]-
paracyclophane 21. A mixture of 4,12-divinyl[2.2]PCP 17 (0.26 g,
.01 mmol), 4-bromo-2,1,3-benzothiadiazole (0.22 g, 1.02 mmol),
Pd(OAc) (23.5 mg, 0.10 mmol), K CO (0.69 g, 4.97 mmol), n-
2H), 2.80 (m, 4H), 3.00 (m, 4H), 3.11 (m, 1H), 3.25 (m, 3H), 3.37 (s,
3H), 3.43 (m, 1H), 6.14 (s, 1H), 6.19 (s, 1H), 6.59 (m, 2H), 6.74 (d, J =
7.8 Hz, 1H), 6.81 (d, J = 7.8 Hz, 1H), 6.94 (m, 2H), 7.01 (d, J = 1.2 Hz,
1H), 7.17 (m, 2H), 7.25 (1H), 7.49 (dd, J = 9.0, 8.4 Hz, 1H), 7.86 (d, J =
4
1
13
9.0 Hz, 1H); C NMR (150 MHz, CDCl ) δ 33.0, 33.6, 35.2, 35.3, 36.0,
2
2
3
3
Bu NBr (0.32 g, 1.00 mmol), and DMF (30 mL) was stirred at 100 °C
4
37.1, 114.0, 119.3, 122.3, 123.3, 123.4, 127.0, 127.2, 127.3, 127.4, 129.6,
J
dx.doi.org/10.1021/jo5020273 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
1
1
33.8, 134.5, 134.6, 135.6, 136.6, 137.2, 137.4, 139.4, 139.5, 141.2, 141.3,
To a toluene solution (40 mL) of 2,3-diaminotoluene was added
43.9, 146.0, 154.9, 155.3; HRMS (FAB-TOF) m/z calcd. for
dropwise SOCl (11.0 mL, 152 mmol) over a period of ca. 3 min with
2
+
C H N S 609.2272 [M ], found 609.2270. Anal. Calcd for
vigorous stirring, and the mixture was refluxed overnight. After cooling
3
9
35
3 2
C H N S : C, 76.81; H, 5.79; N, 6.89. Found: C, 76.85; H, 5.71; N,
to room temperature, water was added to the reaction mixture to quench
3
9
35
3 2
6
.77.
Experimental procedures of the reference compounds 23−25 are also
described.
Synthesis of the Reference Compounds 23−25. 4,12-
Dibromo[2.2]paracyclophane 7. This compound was synthesized
excess SOCl . The toluene was removed, and the residue was purified by
steam-distillation, followed by silica gel column chromatography
2
(hexane, R = 0.13) to give 4-methyl-2,1,3-benzothiadiazole as pale
f
1
yellow liquid (3.38 g, 75% from 2-methyl-6-nitroaniline): H NMR (600
MHz, CDCl ) δ 2.75 (s, 3H), 7.35 (d, J = 6.6 Hz, 1H), 7.49 (dd, J = 9.0,
3
18
2
8
13
according to the reported procedures. To a mixture of [2.2]PCP (5.04
g, 24.2 mmol) and CH Cl (80 mL) was added a CH Cl (20 mL)
solution of Br (3.0 mL, 59 mmol) over a period of ca. 30 min at reflux,
and the mixture was stirred overnight at reflux. The reaction mixture was
quenched by aq. Na SO , and the solution was extracted with CH Cl .
The combined CH Cl extract was dried with Na SO , filtered, and the
filtrate was concentrated under reduced pressure. The concentrate was
purified by recrystallization from CHCl to give 4,12-dibromo[2.2]PCP
6.6 Hz, 1H), 7.83 (d, J = 9.0 Hz, 1H) (lit. δ 2.65, 7.10, 7.30, 7.36.); C
2
2
2
2
NMR (150 MHz, CDCl ) δ 17.9, 119.0, 127.9, 129.5, 131.7, 155.0, 155.4
3
2
8
2
(lit. δ 17.6, 118.8, 127.7, 129.3, 131.5, 154.9, 155.4.); HRMS (EI-
+
TOF) m/z calcd. for C H N S 150.0252 [M ], found 150.0289.
7
6
2
2
3
2
2
A mixture of 4-methyl-2,1,3-benzothiadiazole (1.54 g, 10.3 mmol),
2
2
2
4
NBS (2.20 g, 12.4 mmol), AIBN (85.0 mg, 0.52 mmol), and CH Cl (50
2
2
mL) was refluxed overnight. The reaction mixture was extracted with
CH Cl , and the organic layer was dried with Na SO , filtered, and the
3
2
2
2
4
1
7
as colorless solid (2.19 g, 25%): H NMR (600 MHz, CDCl ) δ 2.85
3
filtrate was concentrated under reduced pressure. The concentrate was
(
m, 2H), 2.94 (m, 2H), 3.16 (m, 2H), 3.50 (m, 2H), 6.44 (d, J = 7.8 Hz,
purified by recrystallization from CHCl to give 4-bromomethyl-2,1,3-
3
18
2
3
1
H), 6.51 (d, J = 1.2 Hz, 2H), 7.14 (dd, J = 7.8, 1.2 Hz, 2H) (lit. δ 2.97,
benzothiadiazole 26 as colorless solid (1.57 g, 67%): mp 91−92 °C
.19, 3.49, 6.43, 6.51, 7.13.); 13C NMR (150 MHz, CDCl ) δ 32.8, 35.4,
2
9
1
3
(lit. 90.5−91.5 °C); H NMR (600 MHz, CDCl ) δ 5.00 (s, 2H), 7.57
3
26.7, 128.3, 134.1, 137.3, 138.5, 141.2.
(
dd, J = 8.4, 6.6 Hz, 1H), 7.65 (d, J = 6.6 Hz, 1H), 7.99 (d, J = 8.4 Hz,
H); C NMR (150 MHz, CDCl ) δ 28.3, 121.9, 129.3, 130.8, 153.4,
55.1; HRMS (FAB-TOF) m/z calcd. for C H BrN S 228.9435 [M +
H ], found 228.9428.
4
-(3-Bromopropyl)-12-{3-(N-carbazolyl)propyl}[2.2]paracyclo-
phane 23. A mixture of 4,12-bis(3-bromopropyl)[2.2]PCP 10 (225 mg,
.50 mmol), carbazole (83.5 mg, 0.50 mmol), n-Bu NBr (82.3 mg, 0.26
13
1
1
3
7
6
2
0
+
4
mmol), toluene (10 mL), and a 2 M aqueous NaOH solution (10 mL)
was refluxed for 2 d. The reaction mixture was extracted with CH Cl ,
the combined CH Cl extract was dried, filtered, and the filtrate was
concentrated under reduced pressure. The concentrate was purified by
SiO column chromatography (hexane/CH Cl , 1/3, R = 0.41) to give
A mixture of 4-bromomethyl-2,1,3-benzothiadiazole 26 (0.69 g, 3.01
2
2
mmol), PPh (0.87 g, 3.31 mmol), and toluene (10 mL) was stirred at
3
2
2
1
00 °C overnight. The precipitate was collected by filtration, and washed
with toluene to give the triphenylphosphonium bromide 27 as colorless
powder (1.48 g, quant.): mp 229−230 °C; H NMR (600 MHz,
CD Cl ) δ 5.92 (d, J = 15.0 Hz, 2H), 7.51 (t, J = 8.4 Hz, 1H), 7.58 (td, J =
1
2
2
2
f
4
-(3-bromopropyl)-12-{3-(N-carbazolyl)propyl}[2.2]PCP 23 as color-
1
2
2
less powder (101 mg, 38%; Scheme 4): mp 181−182 °C; H NMR (600
13
7
.8, 3.6 Hz, 6H), 7.77 (m, 10H), 7.91 (dd, J = 9.0, 3.0 Hz, 1H); C NMR
(
150 MHz, CD Cl ) δ 27.1 (d, J = 48.0 Hz), 117.3, 117.9, 121.0 (d, J =
2
2
Scheme 4. Synthesis of the Reference Compounds, Cz-
9.0 Hz), 121.8 (d, J = 3.0 Hz), 129.6 (d, J = 4.5 Hz), 130.0 (d, J = 13.5
Hz), 132.4 (d, J = 7.5 Hz), 134.3 (d, J = 10.5 Hz), 135.1 (d, J = 3.0 Hz),
1
a
(
CH ) -[2.2]PCP-(CH ) Br 23
2 3 2 3
54.6 (d, J = 58.5 Hz); HRMS (FAB-TOF) m/z calcd. for C H N PS
2
5
20
2
+
4
11.1085 [M − Br ], found 411.1078.
{
3-(10-Methyl-10H-phenothiazinyl)}methyltriphenylphos-
phonium bromide 30. To a mixture of 10-methyl-10H-phenothiazine
4.28 g, 20.1 mmol), DMF (7.8 mL, 100 mmol), and CHCl (50 mL)
(
3
was added dropwise POCl (10.0 mL, 107 mmol) over a period of ca. 3
3
min with vigorous stirring at 0 °C. The mixture was then refluxed
overnight. Water was added slowly to the cooled reaction mixture at 0
°
C to quench excess POCl , and the mixture was extracted with CHCl .
3
3
a
The combined CHCl extract was dried with Na SO , filtered, the
3
2
4
Reagents and conditions: (a) carbazole, n-Bu NBr, toluene, 2 M
4
filtrate was concentrated under reduced pressure, and the concentrate
was purified by silica gel column chromatography (hexane/CH Cl , 2/1
NaOH aq., reflux, 2 d.
2
2
then 1/1, R = 0.03, 0.12) to give 10-methyl-10H-phenothazine-3-
f
carboxyaldehyde 28 as greenish yellow solid (4.16 g, 86%): mp 81−83
MHz, CDCl ) δ 1.97 (quint., J = 7.2 Hz, 2H), 2.05 (quint., J = 7.2 Hz,
3
30
−1 1
°
C (lit. 86−87 °C); IR (Nujol) ν 1684 (CO) cm ; H NMR (600
2
5
1
H), 2.33 (quint., J = 7.2 Hz, 1H), 2.42 (quint., J = 7.2 Hz, 1H), 2.68 (m,
H), 3.00 (m, 1H), 3.05 (m, 3H), 3.31 (m, 3H), 4.26 (m, 2H), 6.06 (s,
H), 6.08 (s, 1H), 6.22 (d, J = 7.8 Hz, 1H), 6.31 (d, J = 7.8 Hz, 1H), 6.36
MHz, CDCl ) δ 3.44 (s, 3H), 6.86 (m, 2H), 6.99 (td, J = 7.2, 1.2 Hz,
3
1
1
H), 7.14 (dd, J = 7.2, 1.2 Hz, 1H), 7.20 (m, 1H), 7.61 (d, J = 1.8 Hz,
H), 7.67 (dd, J = 8.4, 1.8 Hz, 1H), 9.81 (s, 1H); 13C NMR (150 MHz,
(
d, J = 7.8 Hz, 1H), 6.61 (d, J = 7.8 Hz, 1H), 7.22 (t, J = 7.2 Hz, 2H), 7.31
(
d, J = 7.8 Hz, 2H), 7.44 (t, J = 2 Hz, 2H), 8.11 (d, J = 7.8 Hz, 2H); 13
C
CDCl ) δ 35.8, 113.7, 114.8, 122.6, 123.6, 124.0, 127.3, 127.8, 128.0,
3
1
30.4, 131.2, 144.1, 151.1, 190.1; HRMS (FAB-TOF) m/z calcd. for
14 11
NMR (150 MHz, CDCl ) δ 29.2, 31.8, 32.7, 32.9, 33.3, 33.4, 33.6, 33.7,
3
+
C H NOS 241.0561 [M ], found 241.0570.
2.5, 108.7, 118.8, 120.3, 122.9, 125.6, 126.7, 127.0, 133.7, 133.8, 134.3,
To 10-methyl-10H-phenothazine-3-carboxyaldehyde 28 (2.52 g, 10.4
34.8, 137.3, 137.4, 139.3, 139.4, 140.1, 140.4, 140.5; HRMS (FAB-
+
mmol) in MeOH (200 mL) was added NaBH (1.19 g, 31.5 mmol), and
4
34
34
the mixture was stirred at room temperature for 1.5 h. The reaction was
quenched by the addition of water, and extracted with AcOEt. The
organic layer was dried with Na SO , filtered, the filtrate was
Calcd for C H BrN: C, 76.11; H, 6.39; N, 2.61. Found: C, 75.96; H,
34
34
6
.41; N, 2.51.
Synthesis of [2.2]PCP-(CH ) -BTD 24, and Me-PTZ-(CH ) -
2
4
2
2
2 2
[2.2]PCP 25 (Scheme 5). {4-(2,1,3-Benzothiadiazolyl)}methyltri-
concentrated under reduced pressure, and the concentrate was purified
by silica gel column chromatography (CH Cl , R = 0.13) to give 3-
hydroxymethyl-10-methyl-10H-phenothiazine 29 as colorless solid
phenylphosphonium bromide 27. To a mixture of 2-methyl-6-
nitroaniline (4.57 g, 30.0 mmol) and EtOH (100 mL) was added
Pd−C-ethylene diamine adduct (0.21 g), and the mixture was stirred at
room temperature overnight under hydrogen atmosphere (1 atm). The
reaction mixture was filtered through a Celite pad, and the filtrate was
concentrated under reduced pressure to give 2,3-diaminotoluene as
yellow solid. This compound was used for the next reaction without
further purification.
2
2
f
3
0
1
(1.80 g, 71%): mp 138−139 °C (lit. 133−133.5 °C); H NMR (600
MHz, Acetone-d ) δ 3.38 (s, 3H), 4.53 (d, J = 6.0 Hz, 2H), 6.93 (m, 3H),
7.14 (m, 2H), 7.19 (m, 2H); C NMR (150 MHz, Acetone-d ) δ 35.7,
6
13
6
64.0, 114.9, 115.1, 123.2, 123.7, 123.9, 126.1, 126.9, 127.6, 128.5, 137.8,
145.6, 146.9; HRMS (FAB-TOF) m/z calcd. for C H NOS 243.0718
14
13
+
[M ], found 243.0716.
K
dx.doi.org/10.1021/jo5020273 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
a
Scheme 5. Syntheses of [2.2]PCP-(CH ) -BTD 24, Me-PTZ-(CH ) -[2.2]PCP 25
2
2
2 2
a
Reagents and conditions: (a) PPh , toluene, reflux, overnight; (b) NaBH , MeOH, rt; (c) PPh ·HBr, CHCl , reflux; (d) NaHMDS/THF, 0 °C, 30
3
4
3
3
min then THF, rt; (e) NH NH ·H O, diethylene glycol, 100 °C, 1 d.
2
2
2
A mixture of 3-hydroxymethyl-10-methyl-10H-phenothiazine 29
1.80 g, 7.40 mmol), triphenylphosphine hydrobromide (2.54 g, 7.40
to the mixture, and the mixture was stirred at room temperature for 3 h.
The reaction mixture was extracted with AcOEt, and the combined
AcOEt extract was dried with Na SO , filtered, the filtrate was
(
mmol), and CHCl (100 mL) was refluxed overnight. The solvent was
3
2
4
removed under reduced pressure. To the residue was added toluene, and
the precipitate was collected by filtration, and washed with toluene to
give the triphenylphosphonium bromide 30 as pale yellow powder (3.80
concentrated under reduced pressure. The concentrate was purified
by silica gel column chromatography (hexane/CH Cl , 3/1, R = 0.09)
2
2
f
to give 4-[(E)-2-{4-(2,1,3-benzothiadiazolyl)}vinyl][2.2]PCP 32 as
1
1
g, 90%): mp >243 °C (decomp.); H NMR (600 MHz, CD Cl ) δ 3.24
yellow powder (0.11 g, 60%): mp 170−171 °C; H NMR (600 MHz,
2
2
(
1
(
7
3
1
1
1
s, 3H), 5.21 (d, J = 13.8 Hz, 2H), 6.54 (dd, J = 8.4, 2.4 Hz, 1H), 6.65 (s,
H), 6.80 (d, J = 7.8 Hz, 1H), 6.90 (t, J = 7.2 Hz, 1H), 6.96 (m, 1H), 7.01
d, J = 7.2 Hz, 1H), 7.16 (t, J = 7.8 Hz, 1H), 7.63 (m, 6H), 7.73 (m, 6H),
.79 (m, 3H); 13C NMR (150 MHz, CD Cl ) δ 29.9 (d, J = 46.5 Hz),
CDCl ) δ 2.93 (m, 1H), 3.13 (m, 6H), 3.72 (m, 1H), 6.52 (m, 5H), 6.75
3
(dd, J = 7.8, 1.8 Hz, 1H), 6.80 (d, J = 1.2 Hz, 1H), 7.36 (d, J = 16.2 Hz,
1H), 7.64 (dd, J = 8.4, 7.2 Hz, 1H), 7.68 (d, J = 7.2 Hz, 1H), 7.91 (dd, J =
13
8.4, 0.6 Hz, 1H), 8.21 (d, J = 15.6 Hz); C NMR (150 MHz, CDCl ) δ
2
2
3
5.20, 114.1 (d, J = 3.0 Hz), 114.3, 117.4, 118.0, 120.6 (d, J = 7.5 Hz),
22.6 (d, J = 19.5 Hz), 123.6, 126.9, 127.6, 129.3, 130.0 (d, J = 13.5 Hz),
30.7 (d, J = 6.0 Hz), 134.4 (d, J = 10.5 Hz), 135.0 (d, J = 3.0 Hz), 154.2,
45.9; HRMS (FAB-TOF) m/z calcd. for C H NPS 488.1602 [M −
34.2, 34.9, 35.3, 35.5, 119.9, 124.8, 126.7, 129.7, 130.1, 130.3, 131.4,
131.8, 132.4, 132.5, 133.1, 135.0, 137.6, 139.3, 139.4, 140.1, 153.4,
+
155.8; HRMS (FAB-TOF) m/z calcd. for C H N S 368.1347 [M ],
24
20
2
32
27
found 368.1354. Anal. Calcd for C H N S: C, 78.23; H, 5.47; N, 7.60.
24 20
2
+
Br ], found 488.1602.
-Formyl[2.2]paracyclophane 31. To [2.2]PCP (1.05 g, 5.04
mmol) in CH Cl (65 mL) were added successively a 1 M CH Cl
2
Found: C, 78.15; H, 5.46; N, 7.53.
4
4-[2-{4-(2,1,3-Benzothiadiazolyl)}ethyl][2.2]paracyclophane 24. A
mixture of 4-[(E)-2-{4-(2,1,3-benzothiadiazolyl)}vinyl][2.2]PCP 32
(36.9 mg, 0.10 mmol), hydrazine monohydrate (0.31 mL, 5.0 mmol),
and diethylene glycol (10 mL) was stirred at 100 °C overnight. The
reaction was checked by NMR, 80% hydrazine monohydrate (0.31 mL,
5.0 mmol) was additionally added to the reaction mixture because the
starting material was remained, and the mixture was continuously stirred
at the same temperature for 1 d. After cooling to room temperature, the
reaction mixture was extracted with AcOEt. The combined AcOEt
extract was dried with Na SO , filtered, and the filtrate was concentrated
2
2
2
solution of TiCl (10.0 mL, 10.0 mmol) and CH OCHCl (0.66 mL,
4
3
2
7
1
.46 mmol) at 0 °C, and the mixture was stirred at room temperature for
d. The reaction mixture was poured into ice−water, and the mixture
was stirred for 2 h. The reaction mixture was extracted with CH Cl , and
2
2
combined CH Cl extract was dried with Na SO , filtered, the filtrate
2
2
2
4
was concentrated under reduced pressure, and the concentrate was
purified by silica gel column chromatography (hexane/CH Cl , 2/1, R
2
2
f
=
0.03) to give 4-formly[2.2]PCP 31 as colorless powder (0.87 g, 73%):
2
4
31
−1
mp 144−145 °C (lit. 142−145 °C); IR (Nujol) ν 1681 (CO) cm ;
under reduced pressure. The residue was purified by silica gel column
chromatography (hexane/CH Cl , 2/1, R = 0.22) and GPC with
1
H NMR (600 MHz, CDCl ) δ 2.96 (m, 1H), 3.07 (m, 3H), 3.21 (m,
3
2
2
f
2
(
1
(
H), 3.27 (m, 1H), 4.10 (m, 1H), 6.38 (dd, J = 7.8, 1.8 Hz, 1H), 6.43
dd, J = 7.8, 1.8 Hz, 1H), 6.50 (dd, J = 7.8, 1.8 Hz, 1H), 6.56 (dd, J = 7.8,
.8 Hz, 1H), 6.59 (d, J = 7.8 Hz, 1H), 6.73 (dd, J = 7.8, 1.8 Hz, 1H), 7.01
d, J = 1.8 Hz, 1H), 9.95 (s, 1H); 13C NMR (150 MHz, CDCl ) δ 33.6,
CHCl to give 4-[2-{4-(2,1,3-benzothiadiazolyl)}ethyl][2.2]PCP 24 as
3
colorless solid (27.5 mg, 74%). Colorless solids (toluene and MeOH):
1
mp 105−106 °C; H NMR (600 MHz, CD Cl ) δ 2.78 (m, 2H), 3.03
2
2
(m, 8H), 3.20 (m, 1H), 3.26 (m, 1H), 3.46 (m, 1H), 6.22 (s, 1H), 6.39
3
3
1
2
5.0, 35.2, 35.3, 132.2, 132.4, 132.9, 133.3, 136.1, 136.3, 136.6, 138.1,
(d, J = 7.8 Hz, 1H), 6.43 (m, 2H), 6.46 (d, J = 7.8 Hz, 1H), 6.66 (d, J =
1
3
39.5, 140.7, 143.2, 191.9; HRMS (FAB-TOF) m/z calcd. for C H O
7.8 Hz), 7.30 (d, J = 6.6 Hz, 1H), 7.51 (m, 1H), 7.85 (d, J = 9.0 Hz); C
NMR (150 MHz, CD Cl ) δ 33.5, 33.6, 34.2, 34.9, 35.0, 35.3, 119.2,
1
7
16
+
36.1201 [M ], found 236.1182.
-[(E)-2-{4-(2,1,3-Benzothiadiazolyl)}vinyl][2.2]paracyclophane
2. To {4-(2,1,3-benzothiadiazolyl)}methyltriphenylphosphonium
2
2
4
127.4, 128.9, 129.6, 130.6, 132.2, 133.2, 133.4, 134.5, 134.9, 135.7, 137.8,
3
139.6, 140.0, 141.1, 155.0, 155.4; HRMS (FAB-TOF) m/z calcd. for
+
bromide 27 (0.37 g, 0.75 mmol) in THF (5.0 mL) was added 1.1 M
THF solution of sodium hexamethyldisilazide (NaHMDS) (0.70 mL,
C H N S 370.1504 [M ], found 370.1520. Anal. Calcd for
2
4
22
2
C H N S: C, 77.80; H, 5.99; N, 7.56. Found: C, 77.89; H, 5.99; N,
24 22 2
0
.77 mmol) at 0 °C under an Ar atmosphere, and the mixture was
7.66.
continuously stirred at the same temperature for 30 min. 4-
Formly[2.2]PCP 31 (0.12 g, 0.50 mmol) in THF (5.0 mL) was added
Mixture of E/Z Isomers of 4-[2-{3-(10-methyl-10H-phenothia-
zinlyl)}vinyl][2.2]paracyclophane 33. To {3-(10-methyl-10H-
L
dx.doi.org/10.1021/jo5020273 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
phenothiazinyl)}methyltriphenylphosphonium bromide 30 (0.57 g,
the G-COE program, Science for Future Molecular Systems,
Kyushu University, Japan. Computations were carried out using
the computer facilities at the Research Institute for Information
Technology, Kyushu University.
1
.00 mmol) in THF (5.0 mL) was added a 1.1 M THF solution of
sodium hexamethyldisilazide (NaHMDS) (1.0 mL, 1.10 mmol) at 0 °C
under an Ar atmosphere, and the mixture was continuously stirred at the
same temperature for 30 min. 4-Formly[2.2]PCP 31 (0.12 g, 0.50
mmol) in THF (5.0 mL) was added to the mixture, and the mixture was
stirred at room temperature for 3h. The reaction mixture was extracted
with AcOEt, and the organic layer was dried with Na SO , filtered, the
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ASSOCIATED CONTENT
Supporting Information
■
*
S
General experimental methods, electrochemical properties,
1
13
absorption and fluorescence spectral data, H and C NMR
spectra, and theoretical calculations. This material is available
free of charge via the Internet at http://pubs.acs.org.
(
7) (a) Hirayama, D.; Takimiya, K.; Aso, Y.; Otsubo, T.; Hasobe, T.;
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AUTHOR INFORMATION
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Ikemoto, J.; Takimiya, K.; Aso, Y.; Otsubo, T. J. Phys. Chem. B 2004, 108,
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Corresponding Author
*
E-mail: shinmyo@ms.ifoc.kyushu-u.ac.jp.
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The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
■
This work was supported by Management Express Grants for
National Universities Cooperation from MEXT, Japan. We
would like to thank Professors Tetsuro Majima and Mamoru
Fujitsuka of The Institute of Scientific and Industrial Research
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(
SANKEN), Okasa University, Japan, for strong collaboration.
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T.S. gratefully acknowledges the financial support for a Grant-in-
Aid for Scientific Research (C) (No. 26410053) and a Grant-in-
Aid for Scientific Research on Innovative Areas “Organic
Synthesis based on Reaction Integration. Development of New
Methods and Creation of New Substances” (No. 2105) from the
Ministry of Education, Culture, Sports, Science, and Technology,
Japan. T.M. is sincerely thankful for the financial support from
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dx.doi.org/10.1021/jo5020273 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
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2
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-[3.3]PCP-(CH
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(
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2
(
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