7124
A. Merhi et al. / Tetrahedron 69 (2013) 7112e7124
evaporated to dryness. The residue was purified twice by column
chromatography on silica gel using DCM/heptane (1:1) as eluent
then increasing the proportion of DCM. Product 7 was isolated as
a dark red powder when DCM/heptane (3:1) were used. Then, the
obtained product was precipitated in heptane to afford 7 as a pure
product with 25% yield. The reaction was followed by MALDI-TOF
MS as well as by NMR. This new compound 7 is very soluble in
most organic solvents and can be purified by precipitation (DCM/
heptane). Compound 7 behaved well on silica gel chromatography
and was fully characterized by usual solution spectroscopies (NMR,
mass spectrometry) and microanalysis; the hydrogen and carbon
atom-labeling scheme for this monomer is shown in Fig. 3. 1H NMR
by-product 14 was isolated as a purple solid and characterized by
proton NMR and Mass. 1H NMR (400 MHz, CDCl3,
d
in ppm): 9.01 (d,
3
2H, JHH¼4.8 Hz, Hb-pyrrolic), 9.00 (s, 4H, Hb-pyrrolic), 8.95 (d, 2H,
3JHH¼4.8 Hz, Hb-pyrrolic), 8.38 (s, 3H, Hfluorenyl, H1), 8.22 (m, 5H,
2Hphenyl and 3Hfluorenyl, H4), 8.14e8.11 (m, 3H, Hfluorenyl, H3),
3
8.05e8.02 (m, 3H, Hfluorenyl, H5), 7.92 (d, 2H, JHH¼8.0 Hz, Hphenyl),
7.69e7.66 (m, 5H, 2Hphenyl and 3Hfluorenyl, H8), 7.54e7.50 (m,
3Hfluorenyl, H6), 7.44e7.40 (m, 5H, 2Hphenyl and 3Hfluorenyl, H7), 4.18
(s, 6H, 3CH2-fluorenyl). MALDI-TOF MS: calcd for C73H44N4Zn:
1043.54742 [MH]þ, found 1043.0360 [MH]þ.
4.4.2. Compound 5,10,15-(trifluorenyl)-20-(4-phenyl-(diphenyl-ar-
sine))porphyrin 15. Among the obtained fractions from the column
chromatography, the arsine porphyrin 15 was obtained in a purple
solid, always mixed with non-reacted iodo compound 13 or dimer
7. This by-product 15 was characterized by Mass: MALDI-TOF MS:
calcd for C77H51AsN4: 1108.17740 [MH]þ; found 1108.04600 [MH]þ.
(500 MHz, CDCl3,
d in ppm): 9.09 (s, 4H, Hb-pyrrolic), 9.07 (d,
3JHH¼5.7 Hz, 2H, Hb-pyrrolic), 9.05 (s, 4H, Hb-pyrrolic), 9.04 (s, 4H, Hb
-
3
pyrrolic), 9.02 (d, JHH¼5.6 Hz, 2H, Hb-pyrrolic), 8.42 (s, 6H, Hfluorenyl
,
0
0
H1 ), 8.35 (m, 2H, Hphenyl), 8.29 (m, 6H, Hfluorenyl, H4 ), 8.26 (m, 2H,
3
0
Hphenyl), 8.18 (m, 6H, Hfluorenyl, H3 ), 8.06 (d, 6H, JHH¼7.8 Hz,
3
0
H
fluorenyl, H5 ), 8.05 (m, 2H, Hphenyl), 7.71 (d, 6H, JHH¼7.6 Hz,
3
0
0
H
fluorenyl, H8 ), 7.54 (t, 6H, JHH¼6.9 Hz, Hfluorenyl, H6 ), 7.43 (t, 6H,
Acknowledgements
3
0
JHH¼6.5 Hz, Hfluorenyl, H7 ), 7.42 (m, 2H, Hphenyl), 4.22 (s, 12H, 6CH2-
fluorenyl). 13C NMR (CDCl3): 150.4 (m, Cq, C1-4-6-9-11-14-16-19),143.7 (Cq,
The authors are grateful to Dr. S. Sinbandhit (CRMPO) for the
technical assistance and helpful discussions for NMR. The authors
are grateful to Region Bretagne for ARED grant for A.M., MRT for
PhD grant concerning S.D. Partial Funding for the project was ob-
00
00
00
00
C9 ), 141.7 (Cq, C4 ), 141.6 (Cq, C8 ), 141.5 (Cq, C5 ), 134.7 (CB), 134.5
0
0
(CA), 134.0 (Cq, C2 ), 133.4 (C4 ), 132.1 (m, CH, C2-3-7-8-12-13-17-18),
0
0
0
0
0
0
131.3 (C1 ), 130.0 (CB ), 127.0 (C6 and C7 ), 126.8 (CA ), 125.2 (C8 ),
0
0
0
121.6 (m, Cq, C5-10-15-20), 120.2 (C5 ), 117.8 (C3 ), 37.1 (C9 ). Rf on silica
lmax, (ε,
ꢀ
ꢀ
tained from the ‘Universite Europeenne de Bretagne’ (UEB) and
from FEDER by an EPT grant in the ‘MITTSI’ program from RTR
BRESMAT.
plate using DCM/heptane (60:40): 0.36. UVevis
(
10ꢁ3 Mꢁ1 cmꢁ1), CH2Cl2, nm): 281 (150), 428 (479), 513 (10), 555
(37), 597 (16), 643 (w). Anal. Calcd for C132H80N8Zn$3CH2Cl2: C,
77.27, H, 4.13, N, 5.34, found: C, 77.31, H, 4.82, N, 5.02. MALDI-TOF
MS: calcd for C132H80N8Zn: 1841.57974 [MH]þ, found 1841.18810
[MH]þ.
References and notes
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thelot, J. J. Electroanal. Chem. 2005, 583, 92.
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48, 4317.
4.3.3. Synthesis of free dimer 8. This new dimer 8 was obtained
from the mono zinc complex 7 by acidic treatments. To a solution of
1 equiv of dimer 7 (10 mg, 0.005 mmol), in 5 mL of freshly distilled
DCM under argon, was added trifluoroacetic acid in large excess
(TFA, 0.05 mL, 75 mg, 0.66 mmol). Immediately, the dark red DCM
solution turned green. The reaction mixture was stirred for 30 min
at room temperature and was controlled by UVevisible spec-
trometry to be sure that zinc was entirely eliminated from the
porphyrin macrocycle, to obtain the totally free and protonated
porphyrin dimer. Finally, potassium carbonate was added to
neutralize this dark green solution, to obtain the free, but
nonprotonated porphyrin dimer 8. The red solution was stirred for
30 min at room temperature. Then, the residue was filtrated on
silica gel using DCM as eluent to afford neutral 8, as a pure product:
15. Drouet, S.; Paul-Roth, C. O.; Fattori, V.; Cocchi, M.; Williams, J. A. G. New J. Chem.
2011, 35, 438.
a dark red powder with 95% yield. 1H NMR (500 MHz, CDCl3
ppm): 8.94 (m, 16H, Hb-pyrrolic), 8.62 (m, 4H, Hphenyl), 8.32 (s, 6H,
d in
16. Ren, X.; Ren, A.; Feng, J.; Sun, C. J. Photochem. Photobiol., A 2009, 203, 92.
17. Drouet, S.; Merhi, A.; Argouarch, G.; Paul, F.; Mongin, O.; Blanchard-Desce, M.;
Paul-Roth, C. O. Tetrahedron 2012, 68, 98.
18. Merhi, A.; Drouet, S.; Kerisit, N.; Paul-Roth, C. O. Tetrahedron 2012, 68, 7901.
19. Paul-Roth, C.; Rault-Berthelot, J.; Simonneaux, G.; Poriel, C.; Abdalilah, M.;
Letessier, J. J. Electroanal. Chem. 2006, 597, 19.
20. Drouet, S.; Paul-Roth, C.; Simonneaux, G. Tetrahedron 2009, 65, 2975.
21. Drouet, S.; Paul-Roth, C. O. Tetrahedron 2009, 65, 10693.
22. Li, B.; Li, J.; Fu, Y.; Bo, Z. J. Am. Chem. Soc. 2004, 126, 3430.
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25. Gouterman, M. J. Mol. Spectrosc. 1961, 6, 138.
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lands, 1964.
H
fluorenyl, H1), 8.18 (m, 6H, Hfluorenyl, H4), 8.08 (m, 6H, Hfluorenyl, H3),
7.98 (d, 6H, 3JHH¼7.8 Hz, Hfluorenyl, H5), 7.78 (m, 4H, Hphenyl), 7.68 (d,
3
3
6H, JHH¼7.6 Hz, Hfluorenyl, H8), 7.52 (t, 6H, JHH¼6.9 Hz, Hfluorenyl
,
3
H6), 7.43 (t, 6H, JHH¼6.5 Hz, Hfluorenyl, H7), 4.22 (s, 12H, 6CH2-
fluorenyl), ꢁ2.70 (4H, NH).
UVevis (lmax, (ε, 10ꢁ3 Mꢁ1 cmꢁ1), CH2Cl2, nm): compound 8 as
a tetracation [H4PoreH4Por]4D: 268e280, 461, 681; compound 8
as a double free base [H2PoreH2Por]: 268 (181), 426 (522), 521
(26), 557 (15), 595 (5), 650 (4). MALDI-TOF MS: calcd for C132H82N8:
1779.66624 [MH]þ, found 1778.95120 [MH]þ.
28. Drouet, S.; Ballut, S.; Rault-Berthelot, J.; Turban, P.; Paul-Roth, C. Thin Solid Films
2009, 517, 5474.
4.4. Characterization of by-products 14 and 15
29. Owens, J. W.; Smith, R.; Robinson, R.; Robins, M. Inorg. Chim. Acta 1998, 279,
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Lee, S. T.; Wu, S. K. Chem. Phys. Lett. 2003, 382, 561.
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4.4.1. Complex Zn(II)-5,10,15-(trifluorenyl)-20-(4-phenylethynyl-
phenyl)porphyrinato 14. The porphyrin 14 was obtained pure as
a first fraction of the column when using DCM/heptane (1:1). This