Synthesis and electronic properties of trimeric octaethylporphyrin (OEP) derivative connected with diacetylene linkage. A comparative study with vinylene-group connected OEP trimer

References

• Only a few recent articles of the p-electronic extended systems of porphyrin nuclei with various linkages are shown. A.S. Lukas, P.J. Bushard, M.R. Wasielewski, Electron transfer involving nonbonded superexchange interactions in rigid donor–acceptor arrays, J. Phys. Chem. A 106 (2002) 2074–2082;
   Google Scholar
• M.E. ElKhouly, Y. Arai, M. Fujitsuka, O. Ito, Photoinduced electron transfer between metal octaethylporphyrins and fullerenes (C60/C70) studied by laser ash photolysis: electron-mediating and hole-shifting cycles, Phys. Chem. Chem. Phys. 4 (2002) 3322–3329;
   Google Scholar
• E.I. Zenkevich, C. Borczykowski, A.M. Shul’ga, Structure and excited state properties of multiporphyrin arrays formed by supramolecular design, J. Porphyrins Phthalocyanines 7 (2003) 731–754;
   Google Scholar
• D.I. Schuster, P. Cheng, P.D. Jarowski, D.M. Guldi, C.P. Luo, L. Echegoyen, S. Pyo, A.R. Holzwarth, S.E. Braslavsky, R.M. Williams, G. Klihm, Design, synthesis, and photophysical studies of a porphyrin-fullerene dyad with parachute topology; charge recombination in the Marcus inverted region, J. Am. Chem. Soc. 126 (2004) 7257–7270;
   Google Scholar
• N. Hayashi, M. Murayama, K. Mori, A. Matsuda, E. Chikamatsu, K. Tani, K. Miyabayashi, M. Miyake, H. Higuchi, Syntheses and electronic properties of the nickel and palladium complexes of the octaethylporphyrin(M1)-(dihexylbithiophene)n-octaethylporphyrin(M2) system [OEP(M1)-(DHBTh)n-OEP(M2)] connected with the diacetylene linkage. A methodology for molecular design of the particular electronic structure, Tetrahedron 60 (2004) 6363–6383.
   Google Scholar
• A part of this work was preliminarily reported. N. Hayashi, M. Sato, K. Miyabayashi, M. Miyake, H. Higuchi, Synthesis and electronic properties of trinucleic porphyrin derivative connected with diacetylene linkage, JAIST Int. Symp. Nano Technol., Symp. Proc. (2005) 94–95.
   Google Scholar
• G. Eglinton, A.R. Galbraith, Cyclic diynes, Chem. Ind. (1956) 737–738.
   Google Scholar
• H.L. Anderson, Meso-alkynyl porphyrins, Tetrahedron Lett. 33 (1992) 1101–1104
   Google Scholar
• D.P. Arnold, A.W. Johnson, M. Mahendran, Some reactions of mesoformyloctaethylporphyrin, J. Chem. Soc., Perkin Trans. 1 (1978) 366–370.
   Google Scholar
• G.V. Ponomarev, A.M. Shul’ga, First synthesis of ethylenebisporphyrins, Khim. Geterotskil. Soedin. (1986) 278–279.
   Google Scholar
• H. Higuchi, K. Shimizu, J. Ojima, K. Sugiura, Y. Sakata, Synthesis and properties of etheno-bridged porphyrin trimers, Tetrahedron Lett. 36 (1995) 5359–5362.
   Google Scholar
• H. Higuchi, M. Takeuchi, J. Ojima, Mono-, di-, and trimetallic palladium(II) porphyrin trimers with etheno-bridge, Chem. Lett. (1996) 593–594;
   Google Scholar
• H. Higuchi, K. Shimizu, M. Takeuchi, J. Ojima, K. Sugiura, Y. Sakata, Synthesis and properties of tris(octaethylporphyrin)s connected with vinylene groups, Bull. Chem. Soc. Jpn 70 (1997) 1923–1933;
   Google Scholar
• H. Higuchi, M. Shinbo, M. Usuki, M. Takeuchi, Y. Hashegawa, K. Tani, J. Ojima, Synthesis and electronic properties of d8 transition-metal complexes of vinylene-bridged bis- and tris(octaethylporphyr-in)s, Bull. Chem. Soc. Jpn 72 (1999) 1887–1898;
   Google Scholar
• H. Higuchi, M. Takeuchi, Y. Hashegawa, J. Ojima, Synthesis and electronic properties of Ni–Pd–Pt complex of vinylene-bridged tris(octaethylporphyrin), Non-linear Opt. 22 (1999) 333–336;
   Google Scholar
• H. Higuchi, M. Shinbo, M. Usuki, M. Takeuchi, K. Tani, K. Yamamoto, Synthesis and structural and electronic properties of the mixed complexes of vinylene-bridged bis- and tris(octaethylpor-phyrin)s with Ni(II) Pd(II), and Pt(II) ions, Bull. Chem. Soc. Jpn 73 (2000) 1259–1275.
   Google Scholar
• A. Vilsmeier, A. Haack, Uber die Einwirkung von Halogenphosphor auf Alkyl-formanilide. Ein neue Methode zur Darstellung sekundärer und tertiärer p-Alkylamino-benzaldehyde, Ber. 60 (1927) 119–122
   Google Scholar
• E. Campaigne, W.L. Archer, p-Dimethylaminobenzaldehyde, Org. Synth. Coll. 4 (1963) 331–333
   Google Scholar
• H.H. Inhoffen, J.H. Fuhrhop, H. Voigt, H. Brockmann Jr., Formylierung der meso-Kohlenstoffatome von Alkyl-substituierten Porphyrinen, Justus Liebigs Ann. Chem. 695 (1966) 133–143;
   Google Scholar
• M.G.H. Vicente, K.M. Smith, Vilsmeier reactions of porphyrins and chlorins with 3-(dimethylamino)acrolein to give meso-(2-formylvi-nyl)porphyrins: new syntheses of benzochlorins, benzoisobacterio-chlorins, and benzobacteriochlorins and reductive coupling of porphyrins and chlorins using low-valent titanium complexes, J. Org. Chem. 56 (1991) 4407–4418.
   Google Scholar
• The reactions were carried out for 6–7 h at 50–55 8C in 1,2-dichloroethane (20 cm3) using 1.7–2.0!10K2 mmol of the starting materials and 15–20 eq. amount of the Vilsmeier reagent, under the limited conditions of which the monoformylation product from 3 was obtained in 70–75% yield. Also see Experimental part as general procedure for Vilsmeier formylation of 3.
   Google Scholar
• Selected structural properties of 10: FAB-MS; m/z 1850.382 for C113H132N12ONi3 (MWZ1850.376). 1 H NMR (CDCl3); dZ11.503 (1H, s, CHO), 9.465 (1H, s, meso-H in the outer ring), 9.423 (2H, s, meso-H in the outer ring), 9.418 (1H, s, meso-H in the outer ring), 9.370 (2H, s, meso-H in the outer ring), 8.866 (1H, s, meso-H in the central ring formylated), 7.860 (1H, d, JZ16.2, vinylene-H), 7.691 (1H, d, JZ15.6, vinylene-H), 7.232 (1H, d, JZ16.2, vinylene-H), 7.145 (1H, d, JZ15.6, vinylene-H), 3.842–2.835 (48H, m, CH2), 1.829–0.856 (72H, m, CH3).
   Google Scholar
• Selected structural properties of 11: FAB-MS; m/z 1669.965 for C101H96N12ONi3 (MWZ1669.968). 1H NMR (1:1 v/v CDCl3:pyridine-d5); dZ11.758 (1H, s, CHO), 9.551 (2H, d, JZ5.4, pyrrole-H in the central ring), 9.502 (2H, d, JZ5.8, pyrrole-H in the central ring), 9.350 (4H, s, meso-H in the outer ring), 9.322 (2H, s, meso-H in the outer ring), 9.277 (2H, d, JZ5.4, pyrrole-H in the central ring), 9.269 (2H, d, JZ5.8, pyrrole-H in the central ring), 9.065 (1H, s, meso-H in the central ring formylated), 4.266–3.183 (32H, m, CH2), 1.922–0.898 (48H, m, CH3).
   Google Scholar
• Studies on the quantitative analysis of the spectral change of 1 in pyridine and on the theoretical interpretation of the position-selectivity in Vilsmeier monoformylation are now underway. The results will be reported in detail properly, together with an application of the present result to the construction of the Studies on the quantitative analysis of the spectral change of 1 in pyridine and on the theoretical interpretation of the position-p-electronic conjugation systems of the new type such as two-dimensional diacetylene- and vinylene-groups connected OEP oligomers.
   Google Scholar