S. Campidelli et al.
ution into MeOH) gave pure 3 (45 mg, 68% yield) as a brown powder.
1H NMR (300 MHz, CDCl3): d=7.77 (brd, J=7.2 Hz, 2H; arom. H),
7.55 (d, J=8.4 Hz, 2H; arom. H), 4.99 (d, J=9.3 Hz, 1H; H pyrrolidine),
4.93 (s, 1H; H pyrrolidine), 4.26 (d, J=9.6 Hz, 1H; H pyrrolidine), 2.79
(s, 3H; NCH3), 0.24 ppm (s, 9H; SiMe3); FTIR (KBr): n˜ =2948, 2779,
2155, 1500, 1462, 1427, 1331, 1246, 1216, 1122, 1103, 864, 842, 758, 704,
through hydrophobic filter paper (Phase separator Whatman filter) and
evaporated to dryness. Purification of the residue by column chromatog-
raphy (eluent first CH2Cl2, then CH2Cl2/Et2O, 100:5 to 100:8) gave pure 2
(13 mg, 65% yield) as a brown-purple powder. 1H NMR (300 MHz,
C2D2Cl4, 558C): d=9.04 (d, J=4.8 Hz, 4H; arom. H), 8.98 (s, 8H; arom.
H), 8.92 (d, J=4.2 Hz, 4H; arom. H), 8.36 (s, 2H; arom. H), 8.30 (d, J=
7.5 Hz, 4H; arom. H), 8.20–8.05 (m, 16H; arom. H), 7.93 (d, J=8.1 Hz,
2H; arom. H), 7.88 (s, 1H; arom. H), 7.82–7.72 (m, 12H; arom. H), 7.62–
7.55 (br m, 2H; arom. H), 6.94 (brs, 2H; arom. H), 6.85 (brs, 1H; arom.
H), 5.57 (brs, 2H; CH2N), 4.49 (brs, 4H; CH2O), 4.49 (d, J=9.6 Hz, 1H;
H pyrrolidine), 4.31 (s, 1H; H pyrrolidine), 3.67 (d, J=9.6 Hz, 1H; H pyr-
582, 552, 526 cmꢀ1
; UV/Vis (toluene): lmax =328, 432, 703 nm; MS
(MALDI-TOF): m/z calcd for C74H19NSi: 949.13 [MꢀH]+; found: 948.13.
Porphyrin 3: Phenylacetylene (4mL, 0.034 mmol), [CuACHTNUTRGNEUNG(MeCN)4]PF6
(3 mg, 0.008 mmol), 2,6-lutidine (100 mL), and water (1 mL) were added
to a solution of porphyrin 5 (15 mg, 0.017 mmol) in THF (10 mL). The
reaction mixture was frozen and the oxygen was removed by several
vacuum/argon cycles. Finally, the solution was stirred at 608C for 20 h,
then water was added, and the mixture was extracted with CH2Cl2. The
organic phase was filtered through hydrophobic filter paper (Phase Sepa-
rator Whatman filter) and evaporated to dryness. Purification of the resi-
due by column chromatography (eluent CH2Cl2) gave pure 3 (10 mg,
rolidine), 2.65 (s, 3H; NCH3) 1.54 ppm (s, 54H; CACHTNUGTRNEUGN(CH3)3); FTIR (KBr):
n˜ =2954, 2923, 2902, 2863, 1596, 1524, 1492, 1460, 1393, 1362, 1337, 1267,
1205, 1151, 1109, 1067, 1039, 998, 852, 810, 796, 720, 668, 576 cmꢀ1; UV/
Vis (toluene): lmax =428, 553, 591 nm; MS (MALDI-TOF): m/z calcd for
C196H124N18O2Zn2: 2888.87 [M]+; found: 2888.80.
1
60% yield) as a purple powder. H NMR (300 MHz, CDCl3): d=8.04 (d,
J=4.5 Hz, 2H; arom. H), 9.00 (s, 4H; arom. H), 8.95 (d, J=4.8 Hz, 2H;
arom. H), 8.53 (s, 1H; arom. H), 8.43 (d, J=8.4 Hz, 2H; arom. H), 8.21
(d, J=8.4 Hz, 2H; arom. H), 8.16 (d, J=8.1 Hz, 6H; arom. H), 8.05 (d,
J=8.4 Hz, 2H; arom. H), 7.77 (d, J=8.4 Hz, 2H; arom. H), 7.55 (t, J=
7.5 Hz, 2H; arom. H), 7.48–7.40 (m, 1H; arom. H), 1.63 ppm (s, 27H; C-
Acknowledgements
This work was supported by ANR (projects f-DNA ANR-09-NANO-005-
01 and TRANCHANT-ANR 2010 BLAN 1009 4) and by the Region Ile-
de-France through the framework of CꢁNanoIdF, the Nanoscience Com-
petence Center of the Paris Region (projects ElecTubes and TENAPO).
K.-H.L.H. and H.I. acknowledge ANR and CꢁNanoIdF for doctoral and
postdoctoral grants. D.M.G. and C.R.N. acknowledge the Bavarian initia-
tive "Solar Technologies Go Hybrid" and the DFG "Excellence Clus-
ter—Engineering of Advanced Materials".
ACHTUNGTRENNUNG
;
UV/Vis (toluene): lmax =425, 550, 589 nm; MS (MALDI-TOF): m/z calcd
for C64H57N7Zn: 987.40 [M]+; found: 987.42.
Fullerene–porphyrin 1: A 1m TBAF solution in THF (50 mL) was added
to a solution of fullerene 4 (15 mg, 0.015 mmol) in dry THF (20 mL) at
08C under argon. The reaction was stirred for 1 h and then water was
added, and the mixture was extracted with CH2Cl2. The organic phase
was filtered through hydrophobic filter paper (Phase separator Whatman
filter) and evaporated to dryness. The fulleropyrrolidine was used directly
for the coupling reaction without further purification. The fullerene de-
rivative was redispersed in THF (30 mL) and then porphyrin 5 (12 mg,
[2] S. Burghardt, A. Hirsch, B. Schade, K. Ludwig, C. Bçttcher, Angew.
[3] S. Zhou, C. Burger, B. Chu, M. Sawamura, N. Nagahama, M. Toga-
[4] N. Nakashima, T. Ishii, M. Shirakusa, T. Nakanishi, H. Murakami, T.
[5] T. Nakanishi, W. Schmitt, T. Michinobu, D. G. Kurth, K. Ariga,
[8] V. Georgakilas, F. Pellarini, M. Prato, D. M. Guldi, M. Melle-
[9] Y. Hizume, K. Tashiro, R. Charvet, Y. Yamamoto, A. Saeki, S. Seki,
0.013 mmol), [CuACHTUNGTRENNUNG(MeCN)4]PF6 (1.5 mg, 0.004 mmol), 2,6-lutidine (50 mL),
and water (1 mL) were added. The reaction mixture was frozen and the
oxygen was removed by several vacuum/argon cycles. Finally, the solution
was stirred at room temperature for 3 days, then water was added, and
the mixture was extracted with CH2Cl2. The organic phase was filtered
through hydrophobic filter paper (Phase separator Whatman filter) and
evaporated to dryness. Purification of the residue by column chromatog-
raphy (eluent first CH2Cl2, then CH2Cl2/Et2O, 100:3) gave pure 1 (13 mg,
54% yield) as a brown-purple powder. 1H NMR (300 MHz, CDCl3): d=
9.04 (d, J=4.8 Hz, 2H; arom. H), 8.98 (s, 4H; arom. H), 8.94 (d, J=
4.5 Hz, 2H; arom. H), 8.66 (s, 1H; arom. H), 8.38 (d, J=8.4 Hz, 2H;
arom. H), 8.23 (d, J=8.1 Hz, 2H; arom. H), 8.20–8.10 (m, 8H; arom. H),
7.97–7.85 (brs, 2H; arom. H), 7.82–7.71 (m, 6H; arom. H), 4.90 (d, J=
9.9 Hz, 1H; H pyrrolidine), 4.85 (s, 1H; H pyrrolidine), 4.17 (d, J=
9.0 Hz, 1H; H pyrrolidine), 2.86 (s, 3H; NCH3), 1.63 ppm (s, 27H; C-
[10] R. Charvet, Y. Yamamoto, T. Sasaki, J. Kim, K. Kato, M. Takata, A.
[12] G. Fernꢉndez, E. M. Pꢂrez, L. Sꢉnchez, N. Martꢅn, Angew. Chem.
[13] G. Fernꢉndez, E. M. Pꢂrez, L. Sꢉnchez, N. Martꢅn, J. Am. Chem.
[14] T. Nishimura, K. Tsuchiya, S. Ohsawa, K. Maeda, E. Yashima, Y.
[16] C.-L. Wang, W.-B. Zhang, R. M. Van Horn, Y. Tu, X. Gong, S. Z. D.
Cheng, Y. Sun, M. Tong, J. Seo, B. B. Y. Hsu, A. J. Heeger, Adv.
[17] C.-L. Wang, W.-B. Zhang, H.-J. Sun, R. M. Van Horn, R. R. Kulkar-
ni, C.-C. Tsai, C.-S. Hsu, B. Lotz, X. Gong, S. Z. D. Cheng, Adv.
ACHTUNGTRENNUNG
;
(MALDI-TOF): m/z calcd for
C
127H62N8Zn: 1762.44 [M]+; found:
1762.41.
Fullerene–porphyrin 2: A 1m TBAF solution in THF (100 mL) was added
to a solution of fullerene 4 (13 mg, 0.014 mmol) in dry THF (10 mL) at
08C under argon. The reaction was stirred for 1 h, then water was added,
and the mixture was extracted with CH2Cl2. The organic phase was fil-
tered through hydrophobic filter paper (Phase separator Whatman filter)
and evaporated to dryness. The fulleropyrrolidine was used directly for
the coupling reaction without further purification. The fullerene deriva-
tive was redispersed in THF (10 mL) and then compound 6 (14 mg,
0.007 mmol), [CuACHTUNGTRENNUNG(MeCN)4]PF6 (1.5 mg, 0.004 mmol), 2,6-lutidine (50 mL),
and water (1 mL) were added. The reaction mixture was frozen and the
oxygen removed by several vacuum/argon cycles. Finally, the solution
was stirred at room temperature for 4 days, then water was added, and
the mixture was extracted with CH2Cl2. The organic phase was filtered
[19] J. Lenoble, S. Campidelli, N. Maringa, B. Donnio, D. Guillon, N.
&
8
&
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
ÝÝ
These are not the final page numbers!