(5 mL). To this mixture an excess of 1,2-dibromoethane was
added. The resulting mixture was stirred at 50 ꢁC overnight. The
volatiles were then evaporated under reduced pressure, water was
added and the crude product was extracted with CH2Cl2 (40
mL). The combined organic fractions were dried over anhydrous
Na2SO4. After evaporation, the crude product was purified by
silica column chromatography (eluent toluene–heptanes: v/v
8 : 3) to give pure 9 (0.053 g, 98%). 1H NMR (CDCl3): d ¼ 8.76
(m, 8H), 8.02 (d, J ¼ 7.9 Hz, 8H), 7.63 (d, J ¼ 8.1 Hz, 4H), 7.22
(d, J ¼ 8.5 Hz, 2H), 7.15 (d, J ¼ 8.5 Hz, 2H), 4.68 (d, J ¼ 2.2 Hz,
2H), 4.45 (t, J ¼ 6 Hz, 2H), 3.72 (t, J ¼ 6 Hz, 2H), 1.47 (s,
18H), ꢀ2.75 (s, 2H). UV-Vis (NMP) lmax (nm) 425, 527, 562,
601, 656. MALDI-TOF MS C57H51BrN4O2: m/z ¼ 902.32, calcd
902.33 (M+).
Porphyrin 12. To a solution of porphyrin 11 (0.07 g, 0.09
mmol) in CH2Cl2 (15 mL), a solution of Zn(OAc)2, 2H2O (0.19 g,
0.9 mmol) in methanol (3 mL) was added. The reaction mixture
was heated under reflux for 4 h. The volatiles were removed from
the reaction mixture and the crude product was purified by silica
column chromatography (eluent toluene) to give pure (12) (0.075
g, 98%). 1H NMR (CDCl3): d ¼ 8.9 (s, 8H), 8.13 (d, J ¼ 8.5 Hz,
6H), 8.06 (d, J ¼ 8.3 Hz, 2H), 7.35 (d, J ¼ 8.5 Hz, 6H), 7.19 (d,
J ¼ 8.3 Hz, 2H), 4.98 (d, J ¼ 2.3 Hz, 6H). FT-IR (KBr) n (cmꢀ1
)
3281, 2126, 1745, 1603, 1587, 1523, 1505, 1488, 1464, 1372, 1338,
1293, 1217, 1172, 1107, 1070, 1028, 994, 928, 796, 717, 674, 637,
617, 535. UV-Vis (NMP) lmax (nm) 431, 567, 600. MALDI-TOF
MS C53H34N4O4Zn: m/z ¼ 854.12, calcd 854.19 (M+).
Porphyrin 13. Compound 12 (0.07 g, 0.09 mmol) and anhy-
drous potassium carbonate (0.22 g, 1.6 mmol) were dissolved in
DMF (5 mL) under stirring. To this mixture an excess of 1,2-
dibromoethane was added. The resulting mixture was stirred at
50 ꢁC overnight. The volatiles were then evaporated under
reduced pressure, water was added and the mixture was extracted
with CH2Cl2 (50 mL). The combined organic fractions were
dried over anhydrous Na2SO4. After evaporation, the crude
product was purified by silica column chromatography (eluent
Porphyrin 10. A solution of Zn(OAc)2, 2H2O (0.21 g, 1
mmol) in methanol (3 mL) was added to a solution of
porphyrin 9 (0.053 g, 0.05 mmol) in CH2Cl2 (15 mL). The
reaction mixture was heated under reflux for 4 h. The volatiles
were removed from the reaction mixture and 10 was purified by
silica column chromatography (eluent toluene–heptanes: v/v
1
8 : 2) to give pure (10) (0.045 g, 95%). H NMR (CDCl3): d ¼
8.77 (m, 8H), 8 (d, J ¼ 7.9 Hz, 8H), 7.62 (d, J ¼ 8.1 Hz, 4H),
7.21 (d, J ¼ 8.5 Hz, 2H), 7.14 (d, J ¼ 8.5 Hz, 2H), 4.68 (d, J ¼
2.2 Hz, 2H), 4.46 (t, J ¼ 6 Hz, 2H), 3.73 (t, J ¼ 6 Hz, 2H), 1.49
(s, 18H). FT-IR (KBr) n (cmꢀ1) 3300, 2922, 2854, 1748, 1606,
1492, 1462, 1378, 1338, 1243, 1215, 1176, 1108, 1067, 997, 851,
799, 722, 643, 575, 558. UV-Vis (NMP) lmax (nm) 429, 573,
613. MALDI-TOF MS C57H49BrN4O2Zn: m/z ¼ 964.23, calcd
964.24 (M+).
1
toluene–heptanes: v/v 8 : 2) to give pure (13) (0.082 g, 95%). H
NMR (CDCl3): d ¼ 8.9 (s, 8H), 8.13 (d, J ¼ 8.2 Hz, 8H), 7.36 (d,
J ¼ 8.2 Hz, 8H), 5 (d, J ¼ 1.8 Hz, 6H), 4.6 (t, J ¼ 6.2 Hz, 2H), 3.8
(t, J ¼ 6.2 Hz, 2H). FT-IR (KBr) n (cmꢀ1) 3295, 2964, 2925, 2857,
1727, 1603, 1588, 1524, 1505, 1490, 1475, 1372, 1338, 1288, 1260,
1217, 1173, 1107, 1070, 1028, 995, 925, 848, 796, 719, 676, 634,
616, 538. UV-Vis (NMP) lmax (nm) 431, 568, 607. MALDI-TOF
MS C55H37BrN4O4Zn: m/z ¼ 960.13, calcd 960.15 (M+).
Porphyrin 1. Sodium azide (0.97 g, 15 mmol) was added to
compound 4 (0.073ꢁg, 0.07 mmol) in DMF (5 mL). The solution
was stirred at 100 C overnight. The volatiles were evaporated
under reduced pressure, water was added and the crude product
was extracted with CH2Cl2 (50 mL). The combined organic
fractions were dried over anhydrous Na2SO4. After evaporation,
the crude product was purified by silica column chromatography
(eluent toluene–heptanes: v/v 8 : 2) to give pure (1) (0.068 g,
98%). FT-IR (KBr) n(cmꢀ1) 3301, 2963, 2925, 2855, 2117, 1736,
1606, 1506, 1465, 1368, 1339, 1259, 1219, 1174, 1071, 1020, 1008,
796, 699, 647, 540. UV-Vis (NMP) lmax (nm) 430, 575,
610. MALDI-TOF MS C57H49N7O2Zn: m/z ¼ 927.32, calcd
927.29 (M+).
Porphyrin 2. Sodium azide (0.97 g, 15 mmol) was added to
compound 13 (0.067 g, 0.07 mmol) in DMF (5 mL) and the
solution was stirred at 100 ꢁC overnight. The volatiles were then
evaporated under reduced pressure, water was added and the
mixture was extracted with CH2Cl2 (50 mL). The combined
organic fractions were dried over anhydrous Na2SO4. After
evaporation, the crude product was purified by silica column
chromatography (eluent toluene–heptanes: v/v 8 : 2) to give pure
(2) (0.063 g, 98%). FT-IR (KBr) n (cmꢀ1) 3298, 2963, 2924, 2855,
2117, 1736, 1604, 1588, 1524, 1507, 1464, 1368, 1339, 1259, 1219,
1174, 1071, 1020, 1018, 1008, 929, 863, 722, 690, 647, 541. UV-
Vis (NMP) lmax (nm) 431, 573, 600. MALDI-TOF MS
C55H37N7O4Zn: m/z ¼ 923.22, calcd 923.21 (M+).
Porphyrin 11. 4-Propargylbenzaldehyde (4 g, 25 mmol) and 4-
hydroxybenzaldehyde (1 g, 8 mmol) were dissolved in propionic
acid (80 mL) under stirring. The resulting solution was heated to
reflux, and then pyrrole (2.2 mL, 33 mmol) was added dropwise.
After stirring for 1 h at 150 ꢁC, the solution was cooled and then
concentrated. The mixture was precipitated by adding methanol
(50 mL), the precipitate was collected by filtration and washed
with cold methanol. The crude product was purified by silica
column chromatography (eluent toluene) to give our expected
porphyrin (0.38 g, 6%). 1H NMR (CDCl3): d ¼ 8.97 (s, 8H), 8.20
(d, J ¼ 8.4 Hz, 6H), 8.07 (d, J ¼ 8.1 Hz, 2H), 7.36 (d, J ¼ 8.6 Hz,
6H), 7.19 (d, J ¼ 8.3 Hz, 2H), 4.99 (d, J ¼ 2.3 Hz, 6H). UV-Vis
(NMP) lmax (nm) 422, 519, 557, 597, 653. MALDI-TOF MS
C53H36N4O4: m/z ¼ 792.27, calcd 792.28 (M+).
Acknowledgements
This work has been supported by ANR (project TRANCHANT-
ANR 2010 BLAN 1009 4) and by the Region Ile-de-France in the
framework of C’Nano IdF, the nanoscience competence center
of Paris Region (project ElecTubes). IH acknowledges C’Nano
IdF and ANR for postdoctoral grants.
Notes and references
1 Y.-L. Zhao and J. F. Stoddart, Acc. Chem. Res., 2009, 42, 1161.
2 X. Guo, L. Huang, S. O’Brien, P. Kim and C. Nuckolls, J. Am. Chem.
Soc., 2005, 127, 15045.
€
3 A. Star, Y. Lu, K. Bradley and G. Gruner, Nano Lett., 2004, 4, 1587.
J. Mater. Chem.
This journal is ª The Royal Society of Chemistry 2012