CC BY
8Порфирины
Porphyrins
Макрогэтэроцмклы
http://macroheterocycles.isuct.ru
Сообщение
Communication
Synthesis of Gonjugates Based on Fullerene C60 and meso-Tetraphenylporphyrins with Long Chain Substituents
Ekaterina S. Krutikova,@ Natal'ya A. Bragina, and Andrey F. Mironov
Lomonosov Moscow State Academy of Fine Chemical Technology, 119571 Moscow, Russia Corresponding author E-mail: [email protected]
In this paper we report the synthesis of porphyrin-fullerene C60 conjugates by reaction of Prato. Conjugates were determined by H-, 13C-NMR, IR, UV-vis spectroscopy andMALDI-TOF mass spectrometry.
Keywords: Porphyrin, fullerene C60, conjugates, reaction of Prato.
In recent time the functionally substituted fullerenes are of the particular interest; a large number of publications in the world literature is devoted to the synthesis and study of these compounds.[1-10]
Fullerene derivatives have valuable properties and can find practical application in various fields of science and technology as a new chromatographic carriers, liquid crystals, catalysts, dyes, superfirm composites, various conductors, molecular ferromagnets.[1] Application of water-soluble derivatives of fullerene in medicine is rather perspective.[2] Electron donors such as porphyrin, ferrocene, N,N-dimethylaminophenyl, ruthenium(II) trisbipyridine and tetrathiafulvarene, phtalocyanines and others[3-10] have been employed to form fullerene - electron donor type dyads and also can find application in photovoltaic. Since fullerenes linked to porphyrins can produce a long-lived charge-separated state with a high quantum yield in comparison with other known types of donor-acceptor complexes, they are useful candidates to build molecular and supramolecular devices and artificial light energy harvesting systems with unique electronic and magnetic properties.[1,12]
One of the most quickly developing directions is connected with the synthesis and study of fullerene-containing thermotropic liquid crystals (LC) - a new class of nanostructured materials. C60 does not behave as a mesogenic unit. Two approaches have been developed for the preparation
of fullerene-containing liquid crystalline derivatives: in the first one (covalent approach),[13-19] C60 is functionalized with liquid crystalline addends, whereas in the second one (non-covalent approach),[20-21] a supramolecular complex is formed between C60 and mesogenic fragments. It was shown that mesomorphic derivatives of porphyrins can be chosen as mesogenic fragments.[2,22] To the beginning of our research the conjugates on the basis of covalent-associated conjugates of fullerene C60 and mesogenic porphyrins have not been described in the literature.
The present work is devoted to the synthesis of porphyrin-fullerene conjugates based on the fullerene C60 and previously obtained meso-arylsubstituted porphyrins containing long chain alkyl groups.
Conjugates 4, 5 were obtained by the method of Prato.[2] Formylporphyrins with long alkyl substituents were used as aldehyde components. The meso-arylsubstituted porphyrin 1 was synthesized by the monopyrrole condensation method in softconditionsusingpyrroleand4-tetradecyloxybenzaldehyde with 40 % yield.[23] Based on the compound 1 Ni and Cu complexes were obtained (Scheme 1). Formylporphyrins 2, 3 were synthesized by the Vilsmeier method using DMF and POCl3 in CHCl3 during 5-6 h, t = 60°C.
The structure of Ni and Cu complexes of 2-formyl-5,10,15,20-tetrakis-(p-tetradecyloxyphenyl)porphyrin (2, 3) was determined by 1H NMR, IR, UV-vis spectroscopy
R=-OO(CH2)13CH3
Scheme 1. The synthesis of porphyrin-fullerene C60 conjugates. i - 1) NiCl2/Cu(AcO)2, MeOH, CHCl3; 2) DMF and POCl3, CHCl3, 11 - C60,
N-methylglycine, toluene, argon.
130
© ISUCT Publishing Макрогетероциклы /Macroheterocycles 2011 4(2) 130-131
E. S. Krutikova et al.
and MALDI-TOF MS. The IR spectra show the bands at 1671 cm-1 (2) and 1673 cm-1 (3), which correspond to the stretching vibrations of the aldehyde group. In the electronic absorption spectrum of compound 2 a bathochromic shift of the Soret band from 420 nm to 432.5 nm was observed, what confirms the formation of the formyl group. In the 'H NMR spectrum of porphyrin 2 the formyl proton resonated as a distinctive singlet at 5 = 9.29 ppm, whereas the signal of p-proton of the substituted pyrrole ring was observed at 5 = 9.30 ppm. Formyl group causes downfield chemical shift of the signal of the neighboring p-proton due to the growth of the ring current as a result of+C-effect. Other p-protons have chemical shifts at 5 = 8.65-8.80 ppm.
The coupling reaction of aldehydes 2, 3 with ^-methylglycine and C60 in toluene at reflux gave the pyrrolidine-linked porphyrin-fullerene dyads (4, 5). The formation of the conjugate was controlled by TLC (hexane:toluene = 3:1, Rf = 0.75 (2), Rf = 0.80 (3)). Products 4, 5 were isolated by column chromatography on silica gel (hexane:toluene = 3:1, hexane:chloroform = 3:1). The yields of compounds 4, 5 are 20-25 %. The structures of dyads 4, 5 were determined by spectroscopic analysis such as *H, 13C-NMR, IR, UV-vis spectroscopy, and MALDI-TOF MS.
In the UV-vis spectrum of 4 the Soret band (X = 426.5
A v max
nm) is hypsochromically shifted if compared with that of formyl-porphyrin 2 (Xmax = 432.5 nm). The absorption bands of the formyl group are not observed in the IR spectra of compounds 4 and 5. MALDI-TOF MS spectrum exhibit the corresponding M+ ion peak: (m/z) 2298 for 4 and intensive peaks m/z (a.u.): 1574.870 (66427), 1577.034 (14192), 1577.952 (24462), which correspond to the characteristic decomposition products. The *H NMR spectrum of 4 in CDCl3 solution exhibits expected features with correct integration ratios: 5 = 5.30 ppm (1H, s, NCH ), 4.09, 4.12 ppm, (2H, m, NCH2 ), 2.75 ppm ( 3H, s, NCH3 ). The 13C NMR spectrum for 4 shows a multiplicity of signals in the region at 159.80-113.12 ppm arising from fullerene, as well as four peaks assignable to the two pyrrolidine caTbon atoms (69.4, 76.84 ppm) and two sp3 fullerene carbon atoms (68.4, 77.72 ppm).
Thus, novel conjugates 4, 5 were synthesized on the basis of the fullerene C60 and meso-arylsubstituted porphyrin with long chain substituents.
Acknowledgements. This work was supported by RF Ministry for Education and Science (Analytical Departmental Goal-Oriented Program "Development of Scientific Potential of Higher Education» № 2.1.1./9396).
References
1. Meijer M.D., van Klink G.P.M., van Koten G. Coord. Chem. Rev., 2002, 230, 141-163.
2. Fullerenes: Principles and Application (Langa F., Nierengarten J.-F., Eds.). RSC Publishing. 2007.
3. Martin N., Giacalone F., Segura J.L., Guldi D.M., Synth. Met. 2004, 147, 57-61.
4. Hizume Y., Tashiro K., Charvet R., Yamamoto Y., Saeki A., Seki S., Aida T. J. Am. Chem. Soc. 2010, 132, 6628-6629.
5. Takai A., Chkounda M., Eggenspiller A., Gros C. P., Lachkar M., Barbe J.-M., Fukuzumi S. J. Am. Chem. Soc. 2010, 132, 4477-4489.
6. Kaunisto K., Chukharev V., Tkachenko N.V., Efimov A., Lemmetyinen H. J. Phys. Chem. C 2009, 113, 3819-3825.
7. Subbaiyan N.K., Obraztsov I., Wijesinghe C.A., Tran K., Kutner W., D'Souza F. J. Phys. Chem. C. 2009, 113, 89828989.
8. Schuster D.I., Li K., Guldi D.M., Palkar A., Echegoyen L., Stanisky C., Cross R.J., Niemi M., Tkachenko N.V., Lemmetyinen H. J. Am. Chem. Soc. 2007, 129, 15973-15982.
9. D'Souza F., Smith P.M., Zandler M.E., McCarty Mitsunari Itou A.L., Araki Y., Ito O. J. Am. Chem. Soc. 2004, 126, 78987907
10. Kharisov B.I. Ind. Eng. Chem. Res. 2009, 48, 545-571.
11. Marilena Di Valentin J. Am. Chem. Soc. 2004, 126, 51, 1707417086.
12. Bhattacharya S., Nayak S.K., Chattopadhyay S., Banerjee M. J. Solution Chem. 2006, 35, 4.
13. Matsuo Y., Muramatsu A., Hamasaki R., Mizoshita N., Kato T., Nakamura E. J. Am. Chem. Soc. 2004, 126, 432-433.
14. Lenoble J., Campidelli S., Maringa N., Donnio B., Guillon D., Yevlampieva N., Deschenaux R. J. Am. Chem. Soc. 2007, 129, 9941-9952.
15. Matsuo Y., Muramatsu A., Kamikawa Y., Kato T., and Nakamura E., J. Am. Chem. Soc, 2006, 128, 9586-9587.
16. Wei-Shi Li J. Am. Chem. Soc. 2008, 130, 8886-8887.
17. Nakanishi T., Shen Y., Wang J., Yagai S., Funahashi M., Kato T., Fernandes P., Mohwald H., Kurth D.G. J. Am. Chem. Soc. 2008, 130, 9236-9237.
18. Zhong Y., Matsuo Y., Nakamura E. J. Am. Chem. Soc. 2007, 129, 3052-3053.
19 Campidelli S. Tetrahedron 2006, 62, 2115-2122.
20. Drain C.M, Varotto A., Radivojevic I. Chem. Rev. 2009, 109, 1630-1658.
21. Escosura A., Martinez-Diaz M.V., Barbera J., Torres T. J. Org. Chem. 2008, 73, 1475-1480.
22. Sandanayaka A.S.D., Murakami T., Hasobe T. J. Phys. Chem. C. 2009, 113, 42.
23. Fedulova I.N., Bragina N.A., Novikov N.V., Ugol'nikova O.A., Mironov A.F. Russ. J. Bioorg. Chem. 2007, 33, 635-639.
Received 27.04.2011 Accepted 02.06.2011
Макрогетер0циmbl /Macroheterocycles 2011 4(2) 130-131
131
