Full Paper
1,4,8,11,15,18,22,25-Octabutoxy-2,3,9,10,17,17,23,24-octa-
(2-pyrodylthio)phthalocyanine (5a-2H). To a solution of 5a-Mg
(50 mg, 0.025 mmol) in CHCl3 (20 mL), CF3COOH (1.0 mL) was
added slowly and the solution stirred for 15 min under reflux. The
solution was cooled to room temperature and K2CO3 was added
followed by extraction with CHCl3. After evaporation of the solvent,
the residue was purified by column chromatography (Wakogel C-
300HG, CHCl3 and CHCl3/MeOH = 50:1) to produce 5a-2H in 93 %
yield (46 mg); dark green solid; mp: 109–110 °C; 1H NMR (500 MHz,
CDCl3, 25 °C, TMS) δ = 0.75 (s, J = 7.2 Hz, 24H, CH3), 1.30 (sext, J =
7.2 Hz, 16H, CH2), 1.78 (quint, J = 6.8 Hz, 2H, CH2), 4.77 (br, 16H,
CH2), 6.94 (dd, J = 6.4, 5.2 Hz, 8H, Py-H), 7.25 (br, 8H, Py-H), 7.44
(dd, J = 7.2, 1.4 Hz, 8H, Py-H), 8.35 (d, J = 3.6 Hz, 8H, Py-H);
Keywords: Phthalocyanines · Pyridylthio groups ·
Magnesium · Photochemistry · Isobenzofuran
[1] a) A. Jana, M. Ishida, J. P. Park, S. Bähring, J. O. Jeppesen, J. L. Sessler,
Chem. Rev. 2017, 117, 2642–2710; b) S. Singh, A. Aggarwal, N. V. S. D. K.
Bhupathiraju, G. Arianna, K. Tiwari, D. M. Drain, Chem. Rev. 2015, 115,
10261–10306; c) M. Urbani, M. Grätzel, M. Nazeeruddin, T. Torres, Chem.
Rev. 2014, 114, 12330–12396.
[2] a) J. Mack, N. Kobayashi, Chem. Rev. 2011, 111, 281–321; b) F. Dumoulin,
M. Durmuş, V. Ahsen, T. Nyokong, Coord. Chem. Rev. 2010, 254, 2792–
2847.
[3] N. Kobayashi, H. Ogata, N. Nonaka, E. A. Luk'yanets, Chem. Eur. J. 2003,
9, 5123–5134; P. M. Burnham, M. J. Cook, L. A. Gerrard, M. J. Heenet, D. L.
Hughes, Chem. Commun. 2003, 2064–2065; K. Hatsusaka, M. Kimura, K.
Ohta, Bull. Chem. Soc. Jpn. 2003, 76, 781–787; M. N. Yarasir, M. Kandaz,
B. F. Senkal, A. Koca, B. Salih, Polyhedron 2007, 26, 5235–5242; T. B. Ogun-
bayo, T. Nyokong, Polyhedron 2009, 28, 2710–2718; T. Rawling, A.
McDonagh, Coord. Chem. Rev. 2007, 251, 1128–1157.
[4] T. Furuyama, T. Sato, N. Kobayashi, J. Am. Chem. Soc. 2015, 137, 13788–
13791; T. Furuyama, N. Kobayashi, Phys. Chem. Chem. Phys. 2017, 19,
15596–15612.
[5] P. Zimcik, V. Novakova, K. Kopecky, M. Miletin, R. Zeynep, U. Kobak, E.
Svandrlikova, L. Váchová, K. Lang, Inorg. Chem. 2012, 51, 4215–4223; M.
Machacek, A. Cidlina, V. Novakova, J. Svec, E. Rudolf, M. Miletin, R. Kučera,
T. Simunek, P. Zimcik, J. Med. Chem. 2015, 58, 1736–1749.
[6] A. Erdoğmuş, T. Nyokong, J. Mol. Struct. 2010, 977, 26–38; A. Sindelo,
O. L. Osifenko, T. Nyokong, Inorg. Chim. Acta 2018, 476, 68–76; S. Makh-
seed, M. Machacek, W. Alfady, A. Tuhl, M. Vinodh, T. Simunek, V. Novak-
ova, P. Kubat, E. Rudolf, P. Zimcik, Chem. Commun. 2013, 49, 11149–
11151; J. Mikkilä, E. Anaya-Plaza, V. Liljeström, J. Caston, T. Torres, A.
de la Escosura, M. A. Kostiainen, ACS Nano 2016, 10, 1565–1571.
[7] T. Ikeuchi, J. Mack, T. Nyokong, N. Kobayashi, M. Kimura, Langmuir 2016,
32, 11980–11985.
HR-FAB-MS (m/z) 1963.6171 [MH+]; calcd. for C104H107N16O8S8
1963.6224.
=
1,4,8,11,15,18,22,25-Octabutoxy-2,3,9,10,17,17,23,24-octa-
(4-pyridylthio)phthalocyanine (5b-2H). 38 %; dark green crystal;
1
mp: 209–210 °C; H NMR (400 MHz, CDCl3, 25 °C, TMS) δ = 0.83 (t,
J = 7.2 Hz, 24H, CH3), 1.31(sext, J = 7.2 Hz, 16H, CH2), 1.80 (quint,
J = 6.4 Hz, 16H, CH2), 4.78 (t, J = 6.4 Hz, 16H, CH2), 7.10 (dd, J = 4.8,
1.6 Hz, 16H, Py-H), 8.34 (dd, J = 4.8, 1.6 Hz, 16H, Py-H); HR-FAB-MS
(m/z) 1963.6171 [MH+]; calcd. for C104H107N16O8S8 = 1963.6224.
1,4,8,11,15,18,22,25-Octaoctyloxy-2,3,9,10,17,17,23,24-octa-
(2-pyrodylthio)phthalocyanine (6a-2H). 64 %; green solid; m.p. >
300 °C; 1H NMR (500 MHz, CDCl3, 25 °C, TMS) δ = 0.86 (t, J = 7.1 Hz,
24H, CH3), 1.05–1.33 (m, 80H, CH2), 1.80 (quint, J = 7.3 Hz, 16H,
CH2), 4.77 (br, 16H, CH2), 6.92 (ddd J = 5.1 Hz, 8H, Py-H), 7.25 (d, J =
5.1 Hz, 8H, Py-H), 7.43 (ddd, J = Hz, 8H,Py-H), 8.31 (dd, J = 4.6 Hz,
8H, Py-H); HR-FAB-MS (m/z) 2411.1214 [M+ ]; calcd. for
C136H170N16O8S8 = 2411.1153.
[8] L. M. O. Lourenço, P. M. R. Pereira, E. Maciel, M. Válega, F. M. Domingues,
M. R. M. Domingues, M. G. P. M. S. Neves, J. A. S. Cavaleiro, R. Fernandes,
J. P. C. Tomé, Chem. Commun. 2014, 50, 8363–8366.
[9] E. Ranyuk, N. Cauchon, K. Klarskov, B. Guérin, J. E. van Lier, J. Med. Chem.
2013, 56, 1520–1534; H. He, P.-C. Lo, D. K. P. Ng, Chem. Eur. J. 2014, 20,
6241–6245.
[10] a) M. P. Donzello, E. Viola, X. Cai, L. Mannina, C. Rizzoli, G. Ricciardi, C.
Ercolani, K. M. Kadish, A. Rosa, Inorg. Chem. 2008, 47, 3903–3919; b) I.
Manet, F. Manoli, M. P. Donzello, C. Ercolani, D. Vittori, L. Cellai, A. Masi,
S. Monti, Inorg. Chem. 2011, 50, 7403–7411; c) I. Manet, F. Manoli, M. P.
Donzello, E. Viola, A. Masi, G. Andreano, G. Ricciardi, A. Rosa, L. Cellai,
C. Ercolani, S. Monti, Inorg. Chem. 2013, 52, 321–328; d) M. P. Donzello,
G. De Mori, E. Viola, C. Ercolani, G. Ricciardi, A. Rosa, Inorg. Chem. 2014,
53, 8009–8019.
[11] a) H. Li, J. Jensen, F. R. Fronczek, A. G. H. Vicente, J. Med. Chem. 2008,
51, 502–511; b) X. Jia, F.-F. Yang, J. Li, J.-Y. Liu, J.-P. Xue, J. Med. Chem.
2013, 56, 5797–5805; T. T. Tasso, T. Furuyama, N. Kobayashi, Inorg. Chem.
2013, 52, 9206–9215.
1,4,8,11,15,18,22,25-Octabutoxy-2,3,9,10,17,17,23,24-octa-
(2-methylpyridiniumthio)phthalo-cyaninato magnesium (II)
iodide (7a-Mg). Compound 7a-Mg (49 mg, 0.025 mmol) was
placed in a glass reactor and methyl iodide (6.0 mL) was added
under Ar, then the solution was stirred at 40 °C for 24 h. After
evaporation, the residue was washed with acetone and then chloro-
form. The product was dissolved in methanol and filtered. After
evaporation, the product was recrystallized from DMF and CHCl3 to
produce 7a-Mg in 69 % yield (53 mg); green crystal; m.p. > 300 °C;
1H NMR (500 MHz, CD3OD,, 25 °C, TMS) δ = 0.76 (t, J = 7.0 Hz, 24H,
CH3), 1.23–1.38 (m, 16H, CH2), 1.78–1.96 (m, 16H, CH2), 4.54 (s, 24H,
CH3), 5.16 (br, 16H, CH2), 7.74 (t, J = 6.9 Hz, 8H, Py-H), 7.96 (s, 8H,
Py-H), 8.12–8.29 (m, 8H, Py-H), 8.92 (t, J = 6.9 Hz, 8H, Py-H);
MALDI-TOF MS (m/z) 2022.4405 [M–7CH3–8I + Na]+; calcd. for
C105H107N16O8S8Na = m/z 2022.5972.
1,4,8,11,15,18,22,25-Octabutoxy-2,3,9,10,17,17,23,24-octa-
(4-methylpyridiniumthio)phthalo-cyaninato magnesium (II)
iodide (7b-Mg). 56 %; green solid; m.p. > 300 °C; 1H NMR (500 MHz,
CD3OD, 25 °C, TMS) δ = 0.77 (t, J = 7.4 Hz, 24H, CH3), 1.41 (sext, J =
7.4 Hz, 16H, CH2), 1.92 (br, 16H), 4.24 (brs, 24H, CH3), 5.08 (br, 16H
CH2), 8.05 (d, J = 6.9 Hz, 16H, Py-H), 8.60 (d, J = 6.9 Hz, 16HPy-
H), MALDI-TOF MS (m/z) 2022.4849 [M–7CH3–8I + Na]+; calcd. for
C105H107N16O8S8Na = 2022.5972.
[12] a) M. Durmuş, H. Yaman, C. Göl, V. Ashen, T. Nyokong, Dyes Pigm. 2011,
91, 153–156; b) J. B. Pereira, E. F. A. Carvalho, M. A. F. Faustino, R. Fernan-
des, M. G. P. M. S. Neves, J. A. S. Cavaleiro, N. C. M. Gomes, Å. Cunha, A.
Almeida, J. P. C. Tomé, Photochem. Photobiol. 2012, 88, 537–547.
[13] a) T. Kimura, A. Yomogita, T. Matsutani, T. Suzuki, I. Tanaka, Y. Kawai, Y.
Takaguchi, T. Wakahara, T. J. Akasaka, Org. Chem. 2004, 69, 4716–4723;
b) T. Kimura, N. Kanota, K. Matsui, I. Tanaka, T. Tsuboi, Y. Takaguchi, A.
Yomogita, T. Wakahara, S. Kuwahara, F. Nagatsugi, T. Akasaka, Inorg.
Chem. 2008, 47, 3577–3583; c) T. Kimura, N. Murakami, E. Suzuki, T. Fu-
ruyama, T. Nakahodo, H. Fujihara, N. Kobayashi, J. Inorg. Biochem. 2016,
158, 35–44; d) T. Kimura, H. Muraoka, S. Nakajo, S. Ogawa, S. Yamamoto,
N. Kobayash, Eur. J. Org. Chem. 2018, 2018, 1255–1264.
[14] a) E. A. Safonova, A. G. Martynov, S. E. Nafedov, G. A. Kirakosyan, Y. G.
Gobunova, A. Y. Tsivadze, Inorg. Chem. 2016, 55, 2450–2459; b) M. Mat-
sutani, A. Takaki, H. Maekawa, I. Nishiguchi, Sci. Technol. Adv. Mater. 2005,
6, 172–180; c) S. Y. Al-Raqa, Dyes Pigm. 2007, 77, 259–265; d) D. S. Reddy,
Y. E. Ovchinnikov, O. V. Shichkin, Y. T. Struchkov, G. R. Desiraju, J. Am.
Chem. Soc. 1996, 118, 4085–4089.
1,4,8,11,15,18,22,25-Octabutoxy-2,3,9,10,17,17,23,24-octa-
(2-methylpyridiniumthio)phthalo-cyanine iodide (7b-2H). 30 %;
1
green solid; m.p. > 300 °C; H NMR (500 MHz, CD3OD, 25 °C, TMS)
δ = 0.68 (t, J = 7.4 Hz, 24H, CH3), 1.39 (sext, J = 7.4 Hz, 16H, CH2),
1.82 (br, 16H, CH2), 4.15 (s, 24H, CH3), 4.80–5.05 (m, 16H, CH2), 8.12
(br, 16H, Py-H), 8.64 (d, J = 7.2 Hz, 16H, Py-H); MALDI-TOF
MS (m/z) 2024.5093 [M–7CH3–8I
C105H109N16O8S8Na2 = 2023.6175.
+
2Na]+; calcd. for
Eur. J. Inorg. Chem. 2019, 4006–4013
4012
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