Full Paper
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4
00 MHz): d=7.05 (s, 2H; Ar-H), 7.51 (dd, 2H; Ar-H), 7.64 (m, 4H;
7.48 ppm (m, 12H; Ar-H); C NMR (CDCl , 400 MHz): d=24.92,
3
Ar-H), 7.88 (dd, 2H; Ar-H), 7.94 (dd, 2H; Ar-H), 8.01 (d, J = 7.2 Hz,
25.02, 125.45, 125.98, 127.05, 128.11, 128.64, 29.70, 130.23, 130.76,
134.95, 135.50 (m), 136.08, 137.60, 138.7, 140.80 (m), 143.52, 144.56
2
H; Ar-H), 8.16 ppm (s, 2H; Ar-H).
(
1
m), 151.95 ppm (m); MS MALDI-TOF: m/z calcd: 1999.18; found:
126–1130 [MꢀPhenoxyꢀC60].
4
,5-Dithioether-1-naphthyl phthalonitrile: 4,5-Difluorophthaloni-
trile (500 mg, 3.04 mmol), 1-naphthalenethiol (1.05 g, 6.5 mmol),
and potassium carbonate (4.48 g, 32.5 mmol) were dissolved in
DMSO (30 mL) under nitrogen for 48 h. Similar procedure was used
for the purification process as described for compound 4,5-dithioe-
4,5-Hexthioethertolyl SubPc-C60 (3): Compound 3c (90 mg,
0.07 mmol), 60 (151 mg, 0.21 mmol), and sarcosine (31 mg,
0.35 mmol) were mixed and refluxed in toluene (60 mL) for 12 h.
After cooling, the solvent was evaporated to obtain the purple
crude product, which was purified over a silica column. The desired
C
1
thertolyl phthalonitrile as in above. Yield: 55%; H NMR (CDCl3:
4
00 MHz): d=6.68 (s, 2H; Ar-H), 7.64 (m, 6H; Ar-H), 8.01 (m, 4H;
Ar-H), 8.12 (d, J = 7.3 Hz, 2H; Ar-H), 8.26 ppm (m, 2H; Ar-H).
,6-Hexthioethertolyl-SubPc-CHO (1c): 3,6-Dithioethertolyl phtha-
compound was eluted by toluene:ethylacetate (90:10 v/v). Yield:
5
1
0%; H NMR (CDCl : 400 MHz): d=2.40 (m, 18H; methyl-Hs), 2.55
3
3
(s, 3H; fulleropyrrolidine methyl-H), 4.01 (d, J = 7.2 Hz, 1H; fullero-
pyrrolidine-H), 4.50 (s, 1H; fulleropyrrolidine-H), 4.75 (d, J = 7.6 Hz,
lonitrile (500 mg, 1.34 mmol) was refluxed with BCl solution (5 mL)
3
for an hour under nitrogen. After cooling the reaction mixture the
solvent was evaporated to obtain a purple crude subphthalocya-
nine compound. Without further purification, thus obtained crude
compound was mixed with 4-hydroxy benzaldehyde (300 mg,
1
7
H; fulleropyrrolidine-H), 5.25 (m, 2H; Ar-H), 7.15 (d, 2H; Ar-H),
.25 (m, 12H; Ar-H), 7.43 (m, 12H; Ar-H), 8.25 ppm (m, 6H; Ar-H);
1
3
C NMR (CDCl , 400 MHz): d=24.96, 42.88, 70.65, 71.60, 122.65
3
(
(
m), 127.65, 129.15, 129.65, 130.15, 130.65, 132.65, 134.50, 135.65
m), 138.15 (m), 139.15, 140.15 (m), 141.20, 141.75 (m), 143.65,
2
1
.45 mmmol) and dissolved in dry toluene (5 mL) and refluxed for
8 h under nitrogen. After cooling the reaction mixture the solvent
1
44.58 (m), 145.70, 149.15, 151.65, 152.35, 154.65 ppm; MS MALDI-
was evaporated to obtain the crude compound. Thus obtained
crude product was washed with water:methanol mixture (80:20 v/
v ratio; 100 mL) and extracted with DCM. The organic layer was
collected and dried over sodium sulfate. After evaporation of the
organic solvent, the purple crude product was obtained and puri-
TOF: m/z calcd: 1999.18; found: 1126–1131 [MꢀPhenoxyꢀC ].
3,6-Dithioether-2-naphthyl SubPc-C60 (2): Compound 2c (90 mg,
0.06 mmol), 60 (130 mg, 0.18 mmol), and sarcosine (27 mg,
0.30 mmol) were mixed and refluxed in toluene (60 mL) for 12 h.
After cooling, the solvent was evaporated to obtain the purple
crude product, which was purified over a silica column. The desired
6
0
C
fied over a silica column. The desired compound was eluted by
DCM. Yield: 20%; H NMR (CDCl : 400 MHz): d=2.38 (m, 18H;
1
3
methyl-Hs), 5.5 (d, 2H; Ar-H), 6.95 (m, 6H; Ar-H), 7.24 (m, 12H; Ar-
H), 7.34 (m, 2H; Ar-H), 7.65 (m, 12H; Ar-H), 9.66 ppm (s, 1H; -CHO).
compound was eluted by toluene:ethylacetate (90:10 v/v). Yield:
1
40%; H NMR (CDCl
: 400 MHz): d=2.57 (s, 3H; fulleropyrrolidine
3
methyl-H), 3.91 (d, J = 7.5 Hz, 1H; fulleropyrrolidine-H), 4.42 (s, 1H;
fulleropyrrolidine-H), 4.75 (d, J = 7.2 Hz, 1H; fulleropyrrolidine-H),
5.42 (m, 2H; Ar-H), 6.75 (s, 6H; Ar-H), 7.15 (m, 2H; Ar-H), 7.40 (m,
4
,5-Hexthioethertolyl-SubPc-CHO (3c): 4,5-Dithioethertolyl phtha-
lonitrile (500 mg, 1.34 mmol) was used and followed the same
method as described for 1c. Yield: 30%; H NMR (CDCl : 400 MHz):
d=2.50 (s, 18H; methyl-Hs), 5.3 (d, 2H; Ar-H), 7.25 (m, 14H; Ar-H),
1
3
1
3
1
2H; Ar-H), 7.70 (m, 24H; Ar-H), 8.20 ppm (d, 6H; Ar-H). C NMR
(
(
CDCl , 400 MHz): d=25.59, 42.60, 70.44, 125.25, 162.50 (m), 126.95
m), 127.69 (m), 128.19, 128.56, 128.94, 129.25, 131.69, 132.81,
3
7
.45 (d, 12H; Ar-H), 8.35 (s, 6H; Ar-H), 9.60 ppm (s, 1H; -CHO).
3
,6-Dithioether-2-naphthyl SubPc-CHO (2c): 3,6-Dithioether-2-
1
33.56 (m), 134.44 (m), 140.94, 1443.81, 149.94 ppm; MS MALDI-
naphthyl phthalonitrile (500 mg, 1.12 mmol) was used and fol-
lowed the same method as described for 1c. Yield: 20%; H NMR
TOF: m/z calcd: 2215.38; found: 2215.9 [M], 1342–1347 [MꢀPhe-
1
noxyꢀC ].
60
(
CDCl : 400 MHz): d=5.40 (d, 2H; Ar-H), 7.10 (s, 6H; Ar-H), 7.45 (m,
3
4
,5-Dithioether-2-naphthyl SubPc-C60 (4): Compound 4c (90 mg,
1
4H; Ar-H), 7.70 (dd, 12H; Ar-H), 7.80 (dd, 12H; Ar-H), 8.25 (s, 6H;
Ar-H), 9.60 ppm (s, 1H; -CHO).
,5-Dithioether-2-naphthyl SubPc-CHO (4c): 4,5-Dithioether-2-
0
0
.06 mmol), C60 (130 mg, 0.18 mmol), and sarcosine (27 mg,
.30 mmol) were mixed and refluxed in toluene (60 mL) for 12 h.
4
After cooling, the solvent was evaporated to obtain the purple
crude product, which was purified over a silica column. The desired
naphthyl phthalonitrile (500 mg, 1.12 mmol) was used and fol-
lowed the same method as described for 1c. Yield: 25%; H NMR
1
compound was eluted by toluene:ethylacetate (90:10 v/v). Yield:
(
CDCl : 400 MHz): d=5.20 (d, 2H; Ar-H), 7.08 (d, 2H; Ar-H), 7.40 (m,
1
3
4
0%; H NMR (CDCl : 400 MHz): d=2.55 (s, 3H; fulleropyrrolidine
3
1
8H; Ar-H), 7.65 (m, 18H; Ar-H), 7.82 (s, 6H; Ar-H), 8.35 (s, 6H; Ar-
H), 8.40 (d, 6H; Ar-H), 9.50 ppm (s, 1H; -CHO).
,5-Dithioether-1-naphthyl SubPc-CHO (5c): 4,5-Dithioether-1-
methyl-H), 4.01 (d, J = 7.4 Hz, 1H; fulleropyrrolidine-H), 4.50 (s, 1H;
fulleropyrrolidine-H), 4.75 (d, J = 7.6 Hz, 1H; fulleropyrrolidine-H),
5.25 (m, 2H; Ar-H), 7.13 (m, 6H; Ar-H), 7.23 (m, 8H; Ar-H), 7.42 (dd,
6H; Ar-H), 7.52 (m, 6H; Ar-H), 7.72 (m, 6H; Ar-H), 7.81 (d, 6H; Ar-
4
naphthyl phthalonitrile (500 mg, 1.12 mmol) was used and fol-
lowed the same method for 1c. Yield: 20%; H NMR (CDCl3:
1
13
H), 7.92 (m, 6H; Ar-H), 8.40 ppm (m, 6H; Ar-H); C NMR (CDCl3,
4
00 MHz): d=5.10 (d, 2H; Ar-H), 7.08 (d, 2H; Ar-H), 7.55 (m, 18H;
Ar-H), 7.75 (d, 6H; Ar-H), 7.98 (d, 6H; Ar-H), 8.55 (m, 12H; Ar-H),
.40 ppm (s, 1H; -CHO).
,6-Hexthioethertolyl SubPc-C60 (1): Compound 1c (90 mg,
400 MHz): d=21.34, 39.9, 68.26, 123.9, 124.27, 125.37, 126.77 (m),
127.65, 127.95 (m), 128.15, 129.05, 129.27 (m), 29.52 (m), 130.4,
130.65, 131.54, 131.77, 132.77, 134.02, 137.92, 140.15, 140.52,
9
1
41.65 (m), 145.02 (m), 145.90 (m), 150.27 ppm; MS MALDI-TOF: m/
3
z calcd: 2215.38; found: 2215.2 [M], 1342–1347 [MꢀPhenoxyꢀC ].
0
0
.07 mmol), C60 (151 mg, 0.21 mmol), and sarcosine (31 mg,
.35 mmol) were mixed and refluxed in toluene (60 mL) for 12 h.
60
4,5-Dithioether-1-naphthyl SubPc-C (5): Compound 5c (90 mg,
6
0
After cooling, the solvent was evaporated to obtain the purple
crude product, which was purified over a silica column. The desired
0.06 mmol), C60 (130 mg, 0.18 mmol), and sarcosine (27 mg,
0.30 mmol) were mixed and refluxed in toluene (60 mL) for 12 h.
After cooling, the solvent was evaporated to obtain the purple
crude product, which was purified over a silica column. The desired
compound was eluted by toluene:ethylacetate (90:10 v/v). Yield:
1
4
5%; H NMR (CDCl : 400 MHz): d=2.35 (m, 18H; methyl-Hs), 2.55
3
(
s, 3H; fulleropyrrolidine methyl-H), 3.91 (d, J = 7.8 Hz, 1H; fullero-
compound was eluted by toluene:ethylacetate (90:10 v/v). Yield:
1
pyrrolidine-H), 4.40 (s, 1H; fulleropyrrolidine-H), 4.70 (d, J = 7.4 Hz,
35%; H NMR (CDCl : 400 MHz): d=2.40 (s, 3H; fulleropyrrolidine
3
1
6
H; fulleropyrrolidine-H), 5.40 (m, 2H; Ar-H), 6.71 (m, 6H; Ar-H),
.85 (d, 2H; Ar-H), 7.15 (m, 12H; Ar-H), 7.20 (d, 2H; Ar-H),
methyl-H), 4.01 (d, J = 6.9 Hz, 1H; fulleropyrrolidine-H), 4.45 (s, 1H;
fulleropyrrolidine-H), 4.75 (d, J = 7.3 Hz, 1H; fulleropyrrolidine-H),
Chem. Eur. J. 2016, 22, 1 – 12
9
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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