R. K. Dubey et al.
(m, 5H), 1.44–1.23 (m, 20H), 0.87 ppm (m, 6H); MS (ESI-TOF): calcd
J=11.3 Hz, 2H), 4.70–4.40 (m, 5H), 4.39–4.10 (m, 8H), 4.05–3.30 (m,
4H), 2.60–1.90 (m, 10H), 1.87–1.64 (m, 6H), 1.40–1.20 (m, 20H), 0.94–
0.80 ppm (m, 6H); MS (ESI-TOF): calcd for C120H68N4O12: 1757.4867
[M]+; found: 1757.4926.
for C52H57N3O5: 803.4298 [M]+; found: 803.4354.
N,N’-Dioctyl-1,7(6)-bis[2-(benzyloxymethyl)pyrrolidinyl]perylene diimide
(9): 1H NMR (300 MHz, CDCl3, TMS): d=8.63 (s, 1H), 8.52–8.46 (m,
2H), 8.25 (d, J=7.9 Hz, 1H), 8.19 (d, J=7.9 Hz, 1H), 8.07 (d, J=8.2 Hz,
1H), 7.40–7.28 (m, 10H), 4.69–4.56 (m, 6H), 4.28–4.16 (m, 5H), 4.04–
3.89 (m, 3H), 3.86–3.76 (m, 2H), 3.66–3.46 (m, 3H), 2.34–2.10 (m, 6H),
1.82–1.70 (m, 5H), 1.41–1.22 (m, 20H), 0.93–0.84 ppm (m, 6H); MS
(ESI-TOF): calcd for C64H72N4O6: 992.5452 [M]+; found: 992.5453.
Synthesis of N,N’-dioctyl-1,6-bis[2-(ethoxymalonateoxymethyl)pyr
ACHTUNGTRENNUNGrolACHTUNGTRENNUNGidin-
A
R
ACTHUNGTRENNUNyG ACHTUNGTRENNNUG
prepared from N,N’-dioctyl-1,6-bis[2-(hydroxymethyl)pyrrolidinyl]pery-
lene diimide 11 (10.6 mg, 13.1 mmol), Et3N (3.8 mL, 27.3 mmol), and ethyl
malonyl chloride (5.0 mL, 39.0 mmol) following the procedure described
above for compound 12. The crude product was purified by column chro-
matography (silica-60; CHCl3) to afford the purified compound 14
(12.1 mg, 89%) as a deep-blue solid. 1H NMR (300 MHz, CDCl3, TMS):
d=8.69 (d, J=8.1 Hz, 2H), 8.51 (s, 2H), 8.29 (d, J=8.1 Hz, 2H), 4.70–
4.46 (m, 5H), 4.27–4.13 (m, 8H), 4.10–3.90 (m, 2H), 3.80–3.55 (m, 2H),
3.45 (s, 4H), 2.41–2.26 (m, 2H), 2.09–1.91 (brm, 6H), 1.84–1.67 (m, 6H),
1.43–1.21 (m, 25H), 0.95–0.84 ppm (m, 6H); MS (ESI-TOF): calcd for
C60H72N4O12Na: 1063.5044 [M+Na]+; found: 1063.5046.
Synthesis of N,N’-dioctyl-1,7- and -1,6-bis[2-(hydroxymethyl)pyrrolidi-
nyl]perylene-3,4,9,10-tetracarboxy diimides (10 and 11): A 1:1 regioiso-
meric mixture of N,N’-dioctyl-1,7- and -1,6-bis[2-(benzyloxymethyl)pyrro-
lidinyl]perylene diimides 9 (100 mg, 0.10 mmol) was dissolved in dry
CH2Cl2 (10 mL) and the solution was cooled to À788C. BBr3 (1m solu-
tion in CH2Cl2, 210 mL, 0.21 mmol) was then added, and the reaction mix-
ture was stirred at À788C for 45 min. The progress of the reaction was
monitored by TLC analysis of removed aliquots (CHCl3/EtOH, 50:1).
When the starting material had been essentially consumed, the reaction
was quenched by the addition of MeOH (20 mL). Further CH2Cl2
(10 mL) was added and the solution was washed with water (3ꢂ30 mL).
The organic phase was collected, dried over sodium sulfate, and concen-
trated. The crude residue was first purified by column chromatography
on silica-100 (CHCl3 and CHCl3/EtOH, 50:1) to obtain a regioisomeric
mixture of 10 and 11 (52.7 mg, 64.4%). The regioisomers were finally
separated on HPTLC glass plates to yield N,N’-dioctyl-1,7-bis[2-(hy-
Synthesis of DB-1,6-PDI-C60 (15): I2 (5.9 mg, 23.2 mmol) and N,N’-dioc-
tyl-1,6-bis[2-(ethoxymalonateoxymethyl)pyrrolidinyl]perylene diimide 14
(12.1 mg, 11.6 mmol) were added to a clear solution of C60 (9.2 mg,
12.8 mmol) in toluene (170 mL). The resulting solution was stirred for
15 min under argon atmosphere. DBU (9.8 mL, 69.6 mmol) was then
added, and the reaction mixture was stirred for a further 40 min at room
temperature under argon atmosphere. Thereafter, the toluene was re-
moved by rotary evaporation. The solid residue was first purified by
column chromatography (silica-60; CHCl3) and subsequently on HPTLC
glass plates to afford the desired dyad 15 as a blue solid (6.2 mg, 30.4%).
1H NMR (300 MHz, CDCl3, TMS): d=9.14 (s, 1H), 8.67 (d, J=8.1 Hz,
1H), 8.48 (d, J=8.0 Hz, 1H), 8.43 (s, 1H), 7.39 (d, J=8.0 Hz, 1H), 7.32
(d, J=8.1 Hz, 1H), 5.08 (d, J=11.1 Hz, 1H), 5.03–4.89 (m, 2H), 4.80–
4.67 (m, 1H), 4.64–4.48 (m, 2H), 4.32 (d, J=10.8 Hz, 1H), 4.27–4.11 (m,
5H), 4.02–3.36 (m, 6H), 2.60–1.70 (m, 11H), 1.42–1.08 (m, 26H), 0.94–
0.72 ppm (m, 7H); MS (ESI-TOF): calcd for C120H68N4O12: 1757.4867
[M]+; found: 1757.4940.
ACHTUNGTRENNUNGdroxyACHTUNGTRENNUNGmethACHTUNGTRENNUNGyl)pyrrolidinyl]perylene diimide 10 (12.8 mg, 15.6%) as a
dark-green solid and N,N’-dioctyl-1,6-bis[2-(hydroxymethyl)pyrrolidinyl]-
perylene diimide 11 (15.5 mg, 18.9%) as a dark-blue solid.
N,N’-Dioctyl-1,7-bis[2-(hydroxymethyl)pyrrolidinyl]perylene diimide (10):
1H NMR (300 MHz, CDCl3, TMS): d=8.46 (s, 2H), 8.35 (d, J=8.1 Hz,
2H), 7.92 (d, J=8.1 Hz, 2H), 4.45 (brs, 2H), 4.26–4.11 (m, 7H), 4.07–
3.95 (m, 3H), 3.88–3.76 (m, 1H), 3.64–3.47 (m, 2H), 2.95–2.75 (m, 1H),
2.40–2.18 (m, 4H), 2.07–1.88 (m, 4H), 1.80–1.68 (m, 4H), 1.46–1.19 (m,
20H), 0.93–0.79 ppm (m, 6H); MS (ESI-TOF): calcd for C50H60N4O6:
812.4513 [M]+; found: 812.4530.
Synthesis of N,N’-dioctyl-1-pyrrolidinyl-7(6)-[2-(benzyloxymethyl)pyr
idinyl]per lene-3,4,9,10-tetracarboxy diimide (16): N,N’-Dioctyl-1-bromo-
7(6)-[2-(benzyloxymethyl)pyrrolidinyl]perylene diimide (65 mg,
ACHTUNGTRENNUNGrol-
N,N’-Dioctyl-1,6-bis[2-(hydroxymethyl)pyrrolidinyl]perylene diimide (11):
1H NMR (300 MHz, CDCl3, TMS): d=8.68 (d, J=8.0 Hz, 2H), 8.47 (s,
2H), 8.24 (d, J=8.0 Hz, 2H), 4.52 (brs, 2H), 4.29–3.93 (m, 8H), 3.87–
3.50 (m, 4H), 2.90–2.70 (m, 1H), 2.40–1.89 (m, 8H), 1.80–1.69 (m, 6H),
1.43–1.20 (m, 20H), 0.94–0.80 ppm (m, 6H); MS (ESI-TOF): calcd for
C50H60N4O6: 812.4513 [M]+; found: 812.4550.
A
R
ACTHUNGTRENNUNyG ACHTUNGTRENNNUG
7
0.07 mmol) was dissolved in pyrrolidine (10 mL) and the solution was
stirred for 8 h at 608C in a closed vial. The progress of the reaction was
followed by TLC analysis of removed aliquots. When the starting materi-
al had been essentially consumed, the reaction was quenched by the addi-
tion of water (30 mL). The product was extracted with CH2Cl2 (50 mL)
and the organic phase was washed with several portions of water to com-
pletely remove the pyrrolidine. The organic phase was collected, dried
over sodium sulfate, and concentrated. The crude residue was purified by
column chromatography (silica-60; CH2Cl2) to afford the desired product
Synthesis of N,N’-dioctyl-1,7-bis[2-(ethoxymalonateoxymethyl)
yl]per lene-3,4,9,10-tetracarboxy diimide (12): In a typical reaction, N,N’-
dioctyl-1,7-bis[2-(hydroxymethyl)pyrrolidinyl]perylene diimide 10
ACHTUNGTRENNUpGN yrACHTUNRTEGGrNNUN olACHTUNGTRENiNUGN din-
A
ACHTUNGTRENNUNGyACHTUNGTRENNUNG
(12.8 mg, 15.8 mmol) was dissolved in CH2Cl2 (12 mL) and the solution
was cooled in an ice bath. Et3N (6.6 mL, 47.4 mmol) and ethyl malonyl
chloride (6.1 mL, 47.4 mmol) were then added and the reaction mixture
was stirred for 3 h at room temperature. Thereafter, the solvent was re-
moved by rotary evaporation and the solid residue was chromatographed
on silica-60, eluting with CHCl3, to afford 12 (13.8 mg, 84.1%) as a green
solid. 1H NMR (300 MHz, CDCl3, TMS): d=8.66 (s, 2H), 8.49 (d, J=
8.1 Hz, 2H), 8.14 (d, J=8.1 Hz, 2H), 4.75–4.51 (m, 4H), 4.26–4.14 (m,
8H), 3.76–3.58 (m, 3H), 3.48 (s, 4H), 2.44–2.12 (m, 3H), 2.08–1.92 (m,
4H), 1.84–1.67 (m, 6H), 1.43–1.20 (m, 28H), 0.93–0.78 ppm (m, 6H); MS
(ESI-TOF): calcd for C60H72N4O12: 1040.5146 [M]+; found: 1040.5170.
16 (45.1 mg, 64%) as
a
regioisomeric mixture. 1H NMR (300 MHz,
CDCl3, TMS): d=8.65 (d, J=8.2 Hz, 0.14H), 8.55 (s, 0.63H), 8.51–8.46
(brm, 0.21H), 8.41 (brs, 0.21H), 8.38–8.31 (m, 1H), 8.30–8.15 (m, 2H),
8.00 (d, J=8.2 Hz, 0.83H), 7.81 (d, J=8.4 Hz, 0.1H), 7.48 (d, J=7.9 Hz,
0.77H), 7.43–7.29 (m, 4H), 6.90–6.30 (m, 1H), 4.82–4.51 (m, 2H), 4.32–
4.15 (m, 4H), 4.10–3.45 (m, 6H), 2.40–1.90 (m, 7H), 1.86–1.71 (m, 5H),
1.53–1.18 (m, 20H), 0.93–0.82 ppm (m, 6H); MS (ESI-TOF): calcd for
C56H64N4O5: 872.4877 [M]+; found: 872.4965.
Synthesis of N,N’-dioctyl-1-pyrrolidinyl-7-[2-(hydroxymethyl)pyr
yl]per lene-3,4,9,10-tetracarboxy diimide (17) and N,N’-dioctyl-1-pyr
idinyl-6-[2-(hydroxymethyl)pyrrolidinyl]perylene-3,4,9,10-tetracarboxy di-
imide (18): N,N’-Dioctyl-1-pyrrolidinyl-7(6)-[2-(benzyloxymethyl)pyrroli-
ACHTUNGTRENNUNGrolACHTUNGTRENNUNG
A
N
G
ACHTUNGTRENNUNG
Synthesis of DB-1,7-PDI-C60 (13): I2 (3.5 mg, 13.8 mmol) and N,N’-dioc-
tyl-1,7-bis[2-(ethoxymalonateoxymethyl)pyrrolidinyl]perylene diimide 12
A
E
N
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
(7.1 mg, 6.8 mmol) were added to
a clear solution of C60 (5.3 mg,
dinyl]perylene diimide 16 (270.0 mg, 0.31 mmol) was dissolved in dry
CH2Cl2 (100 mL). The solution was cooled in an ice bath for 30 min
under an inert atmosphere. BBr3 (1m solution in CH2Cl2, 1.1 mL,
1.1 mmol) was then added in three portions at intervals of 20 min. The
progress of the reaction was closely monitored by TLC analysis of re-
moved aliquots. After complete consumption of the starting material, the
reaction was quenched by the addition of MeOH (50 mL). The organic
phase was washed with water (2ꢂ100 mL), dried over sodium sulfate,
and concentrated. The green solid residue was purified by column chro-
matography (silica-60; CHCl3) to afford a mixture of the desired products
7.4 mmol) in toluene (100 mL). The resulting solution was stirred for
15 min at room temperature under argon atmosphere. DBU (5.7 mL,
40.4 mmol) was then added, and the reaction mixture was stirred for a fur-
ther 40 min at room temperature under argon atmosphere. Thereafter,
the toluene was removed by rotary evaporation. The solid green residue
was first purified by column chromatography (silica-60; CHCl3) and sub-
sequently on HPTLC glass plates eluting with CHCl3 to afford the de-
sired dyad 13 as a green solid (4.5 mg, 37.6%). 1H NMR (300 MHz,
CDCl3, TMS): d=9.67 (d, J=8.2 Hz, 1H), 9.02 (s, 1H), 8.59 (d, J=
8.0 Hz, 1H), 8.38 (s, 1H), 8.41–8.27 (m, 2H), 5.34–5.16 (m, 1H), 4.85 (d,
&
14
&
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
ÝÝ
These are not the final page numbers!