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A Pd(II)-hydroxyporphycene: synthesis, characterization, and photoinduced proton-coupled electron transfer

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Abstract

A Pd(II) complex, Pd(TPrPc-OH) (1, TPrPc-OH = 9-hydroxy-2,7,12,17-tetrapropylporphycenato dianion), has been synthesized and characterized. 1H NMR spectroscopy revealed that compound 1 exists as its enol form in solution. The H atom of the hydroxy group in 1 was exchanged with deuterium on addition of ethanol-d 6. UV–visible spectra showed a red shift of the Q band of 1 in THF compared with that of the acetoxy derivative Pd(TPrPc-OAc) (2, TPrPc-OAc = 9-acetoxy-2,7,12,17-tetrapropylporphycenato dianion). The pK a value of the hydroxy group in 1 was determined, by means of a UV–visible titration experiment, to be 10.56. A cyclic voltammogram of 1 in a mixture of THF and Britton–Robinson buffered aqueous solution revealed one-electron and one-proton coupled transfer in the oxidation process in the pH range from 2.7 to 10.5, which was identified by pH-varying experiments and the Pourbaix diagram. Transient absorption spectroscopy revealed that an electron-transfer reaction occurred from the triplet excited-state of 1 to 2,3,5,6-tetramethyl-1,4-benzoquinone (duroquinone, DQ) upon pulse laser irradiation at 532 nm. Such an intermolecular photoinduced electron-transfer reaction was not observed between the Ni analog, Ni(TPrPc-OH), and DQ. The reaction rate constant, k q, was indicative of a kinetic isotope effect with k q(H)/k q(D) = 1.7, supporting the belief that the exited-state electron transfer from 1 to DQ is accompanied by proton transfer.

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References

  1. E. Vogel, M. Köcher, H. Schmickler, J. Lex, Porphycene—a novel porphyrin isomer. Angew. Chem. Int. Ed. Engl. 25, 257–259 (1986)

    Article  Google Scholar 

  2. E. Vogel, M. Balci, K. Pramod, P. Koch, J. Lex, O. Ermer, 2,7,12,17-Tetrapropylporphycene–counterpart of octaethylporphyrin in the porphycene series. Angew. Chem. Int. Ed. Engl. 26, 928–931 (1987)

    Article  Google Scholar 

  3. D. Sanchez-Garcia, J.L. Sessler, Porphycene: synthesis and derivatives. Chem. Soc. Rev. 37, 215–232 (2008)

    Article  CAS  Google Scholar 

  4. J.P. Gisselbrecht, M. Gross, M. Koecher, M. Lausmann, E. Vogel, Redox properties of porphycenes and metalloporphycenes as compared with porphyrins. J. Am. Chem. Soc. 112, 8618–8620 (1990)

    Article  CAS  Google Scholar 

  5. C. Bernard, J.P. Gisselbrecht, M. Gross, E. Vogel, M. Lausmann, Redox properties of porphycenes and metalloporphycenes. A comparison with porphyrins. Inorg. Chem. 33, 2393–2401 (1994)

    Article  CAS  Google Scholar 

  6. F. D’Souza, P.L. Boulas, A.M. Aukauloo, R. Guilard, M. Kisters, E. Vogel, K.M. Kadish, Electrochemical, UV/visible, and EPR characterization of metalloporphycenes containing first-row transition metals. J. Phys. Chem. 98, 11885–11891 (1994)

    Article  Google Scholar 

  7. F. D’Souza, P.L. Boulas, M. Kisters, L. Sambrotta, A.M. Aukauloo, R. Guilard, K.M. Kadish, Effect of peripheral substitution and extended conjugation on the redox potentials of nickel porphycenes. Inorg. Chem. 35, 5743–5746 (1996)

    Article  Google Scholar 

  8. D.M. Guldi, P. Neta, E. Vogel, Radiolytic reduction of tetrapropylporphycene and its iron, cobalt, nickel, copper, and tin complexes. J. Phys. Chem. 100, 4097–4103 (1996)

    Article  CAS  Google Scholar 

  9. J. Hasegawa, K. Takata, T. Miyahara, S. Neya, M.J. Frisch, H. Nakatsuji, Excited states of porphyrin isomers and porphycene derivatives: a SAC-CI study. J. Phys. Chem. A 109, 3187–3200 (2005)

    Article  CAS  Google Scholar 

  10. W.A. Oertling, W. Wu, J.J. López-Garriga, Y. Kim, C.K. Chang, Optical absorptions and Raman scattering of metalloporphycenes reveal electronic and vibronic properties distinct from those of metalloporphyrins. J. Am. Chem. Soc. 113, 127–134 (1991)

    Article  CAS  Google Scholar 

  11. S.E. Braslavsky, M. Müller, D.O. Mártire, S. Pörting, S.G. Bertolotti, S. Chakravorti, G. Koç-Weier, B. Knipp, K. Schaffner, Photophysical properties of porphycene derivatives (18π porphyrinoids). J. Photochem. Photobiol. B: Biol. 40, 191–198 (1997)

    Article  CAS  Google Scholar 

  12. H. Shimakoshi, T. Baba, Y. Iseki, I. Aritome, A. Endo, C. Adachi, Y. Hisaeda, Photophysical and photosensitizing properties of brominated porphycenes. Chem. Commun. 2882–2884 (2008)

  13. D. Maeda, H. Shimakoshi, M. Abe, Y. Hisaeda, Syntheses and photophysical behavior of porphyrin isomer Sn(IV) complexes. Inorg. Chem. 48, 9853–9860 (2009)

    Article  CAS  Google Scholar 

  14. M. Taneda, D. Maeda, H. Shimakoshi, M. Abe, Y. Hisaeda, Preparation and photosensitizing properties of 2,7,12,17-tetra-n-propylporphycenatotin(IV) dihalide complexes. Bull. Chem. Soc. Jpn. 83, 667–671 (2010)

    Article  CAS  Google Scholar 

  15. M.W. Renner, A. Forman, W. Wu, C.K. Chang, J. Fajer, Electrochemical, theoretical, and ESR characterizations of porphycenes. The π anion radical of nickel(II) porphycene. J. Am. Chem. Soc. 111, 8618–8621 (1989)

    Article  CAS  Google Scholar 

  16. C.J. Fowler, J.L. Sessler, V.M. Lynch, J. Waluk, A. Gebauer, J. Lex, A. Heger, F. Zuniga-y-Rivero, E. Vogel, Metal complexes of porphycene, corrphycene, and hemiporphycene: stability and coordination chemistry. Chem. Eur. J. 8, 3485–3496 (2002)

    Article  CAS  Google Scholar 

  17. T. Okawara, M. Abe, H. Shimakoshi, Y. Hisaeda, Redox gradations in ruthenium porphycene complexes and the porphyrin analogs: axial and macrocyclic ligand effects. Chem. Lett. 37, 906–907 (2008)

    Article  CAS  Google Scholar 

  18. L. Cuesta, E. Karnas, V.M. Lynch, P. Chen, J. Shen, K.M. Kadish, K. Ohkubo, S. Fukuzumi, J.L. Sessler, Metalloporphycenes: synthesis and characterization of (pentamethylcyclopentadienyl)ruthenium sitting-atop and π-complexes. J. Am. Chem. Soc. 131, 13538–13547 (2009)

    Article  CAS  Google Scholar 

  19. D. Maeda, H. Shimakoshi, M. Abe, Y. Hisaeda, Synthesis and photochemical properties of a new molybdenum porphycene complex. Dalton Trans. 140–145 (2009)

  20. K. Aoki, T. Goshima, Y. Kozuka, Y. Kawamori, N. Ono, Y. Hisaeda, H.D. Takagi, M. Inamo, Electron transfer reaction of porphyrin and porphycene complexes of Cu(II) and Zn(II) in acetonitrile. Dalton Trans. 119–125 (2009)

  21. R. Bonnett, Photosensitizers of the porphyrin and phthalocyanine series for photodynamic therapy. Chem. Soc. Rev. 24, 19–33 (1995)

    Article  CAS  Google Scholar 

  22. J.C. Stockert, M. Canete, A. Juarranz, A. Vallanueva, R.W. Horobin, J.I. Borrell, J. Teixido, S. Nonell, Porphycenes: facts and prospects in photodynamic therapy of cancer. Curr. Med. Chem. 14, 997–1026 (2007)

    Article  CAS  Google Scholar 

  23. T. Matsuo, H. Dejima, S. Hirota, D. Murata, H. Sato, T. Ikegami, H. Hori, Y. Hisaeda, T. Hayashi, Ligand binding properties of myoglobin reconstituted with iron porphycene: unusual O2 binding selectivity against CO binding. J. Am. Chem. Soc. 126, 16007–16017 (2004)

    Article  CAS  Google Scholar 

  24. T. Hayashi, D. Murata, M. Makino, H. Sugimoto, T. Matsuo, H. Sato, Y. Shiro, Y. Hisaeda, Crystal structure and peroxidase activity of myoglobin reconstituted with iron porphycene. Inorg. Chem. 45, 10530–10536 (2006)

    Article  CAS  Google Scholar 

  25. O. Arad, N. Rubio, D. Sánchez-García, J.I. Borrell, S. Nonell, Asymmetric porphycenes: synthesis and photophysical properties of 9-substituted 2,7,12,17-tetraphenylporphycenes. J. Porphyrins Phthalocyanines 13, 376–381 (2009)

    Article  CAS  Google Scholar 

  26. E. Vogel, P. Koch, X.-L. Hou, J. Lex, M. Lausmann, M. Kisters, M.A. Aukauloo, P. Richard, R. Guilard, New porphycene ligands: octaethyl- and etioporphycene (OEPc and EtioPc)—tetra- and pentacoordinated zinc complexes of OEPc. Angew. Chem. Int. Ed. Engl. 32, 1600–1604 (1993)

    Article  Google Scholar 

  27. K.S. Anju, S. Ramakrishnan, A.P. Thomas, E. Suresh, A. Srinivasan, 9,10,19,20-Tetraarylporphycenes. Org. Lett. 10, 5545–5548 (2008)

    Article  CAS  Google Scholar 

  28. T. Baba, H. Shimakoshi, Y. Hisaeda, Synthesis and simple separation of β-pyrrole sulfonated porphycenes. Tetrahedron Lett. 45, 5973–5975 (2004)

    Article  CAS  Google Scholar 

  29. M. Gil, J. Jasny, E. Vogel, J. Waluk, Ground and excited state tautomerization in 9-acetoxy-2,7,12,17-tetra-n-propylporphycene. Chem. Phys. Lett. 323, 534–541 (2000)

    Article  CAS  Google Scholar 

  30. P. Fita, P. Garbacz, M. Nejbauer, C. Padzewicz, J. Waluk, Ground and excited state double hydrogen transfer in symmetric and asymmetric potentials: comparison of 2,7,12,17-tetra-n-propylporphycene with 9-acetoxy-2,7,12,17-tetra-n-propylporphycene. Chem. Eur. J. 17, 3672–3678 (2011)

    Article  CAS  Google Scholar 

  31. H. Shimakoshi, T. Baba, Y. Iseki, A. Endo, C. Adachi, M. Watanabe, Y. Hisaeda, Photosensitizing properties of the porphycene immobilized in sol–gel derived silica coating films. Tetrahedron Lett. 49, 6198–6201 (2008)

    Article  CAS  Google Scholar 

  32. T. Okawara, M. Abe, H. Shimakoshi, Y. Hisaeda, Hydroxy-functionalized porphycenes: structure, spectroscopy, and electrochemistry. Bull. Chem. Soc. Jpn. 84, 718–728 (2011)

    Article  CAS  Google Scholar 

  33. R. Bonnett, M.J. Diasdale, G.F. Stephenson, The meso-reactivity of porphyrins and related compounds. Part IV. Introduction of oxygen functions. J. Chem. Soc. (C) 564–570 (1969)

  34. C–.C. Hsieh, C.-M. Jiang, P.-T. Chou, Recent experimental advances on excited-state intramolecular proton coupled electron transfer reaction. Acc. Chem. Res. 43, 1364–1374 (2010)

    Article  CAS  Google Scholar 

  35. S. Hammes-Schiffer, Theory of proton-coupled electron transfer in energy conversion processes. Acc. Chem. Res. 42, 1881–1889 (2009)

    Article  CAS  Google Scholar 

  36. M.K. Ludlow, A.V. Soudackov, S. Hammes-Schiffer, Theoretical analysis of the unusual temperature dependence of the kinetic isotope effect in quinol oxidation. J. Am. Chem. Soc. 131, 7094–7102 (2009)

    Article  CAS  Google Scholar 

  37. D.K. Palit, Photophysics and excited state relaxation dynamics of p-hydroxy and p-amino-substituted benzophenones: a review. Res. Chem. Intermed. 31, 205–225 (2005)

    Article  CAS  Google Scholar 

  38. C. Costentin, Electrochemical approach to the mechanistic study of proton-coupled electron transfer. Chem. Rev. 108, 2145–2179 (2008)

    Article  CAS  Google Scholar 

  39. S. Prashanthi, P.R. Bangal, Reductive quenching of pyridine linked porphyrins by phenol: a case of proton coupled electron transfer. Chem. Commun. 1757–1759 (2009)

  40. E.R. Young, J. Rosenthal, J.M. Hodgkiss, D.G. Nocera, Comparative PCET study of a donor-acceptor pair linked by ionized and nonionized asymmetric hydrogen-bonded interfaces. J. Am. Chem. Soc. 131, 7678–7684 (2009)

    Article  CAS  Google Scholar 

  41. D. Maeda, H. Shimakoshi, M. Abe, M. Fujitsuka, T. Majima, Y. Hisaeda, Synthesis of a novel Sn(IV) porphycene-ferrocene triad linked by axial coordination and solvent polarity effect in photoinduced charge separation process. Inorg. Chem. 49, 2872–2880 (2010)

    Article  CAS  Google Scholar 

  42. M. Fujitsuka, H. Shimakoshi, S. Tojo, L. Cheng, D. Maeda, Y. Hisaeda, T. Majima, Electron transfer in the supramolecular donor-acceptor dyad of zinc porphycene. J. Phys. Chem. A 113, 3330–3335 (2009)

    Article  CAS  Google Scholar 

  43. A. Berman, A. Michaeli, J. Feitelson, M.K. Bowman, J.R. Norris, H. Levanon, E. Vogel, P. Koch, Photophysics and photoinduced-electron-transfer reactions of zinc and free-base octaethylporphycenes. J. Phys. Chem. 96, 3041–3047 (1992)

    Article  CAS  Google Scholar 

  44. F. D’Souza, G.R. Deviprasad, M.S. Rahman, J. Choi, Self-assembled porphyrin-C60 and porphycene-C60 complexes via metal axial coordination. Inorg. Chem. 38, 2157–2160 (1999)

    Article  Google Scholar 

  45. J. Waluk, E. Vogel, Excited state tautomerization in porphycenes studied by polarized spectroscopy. J. Lumin. 60, 867–869 (1990)

    Article  Google Scholar 

  46. M. Toporowicz, H. Ofir, H. Levanon, E. Vogel, M. Köcher, K. Pramod, R.W. Fessenden, Triplet state of metalloporphycenes: ZnPCl, PdPC2, PtPC2, and NiPC2. Photochem. Photobiol. 50, 37–43 (1989)

    Article  CAS  Google Scholar 

  47. E. Vogel, M. Müller, O. Halpern, A.D. Cross, Derivatives of porphycene for photodynamic therapy of cancer. U.S. Patent 5 244 671 (1996)

    Google Scholar 

  48. M.H.V. Huynh, T.J. Meyer, Proton-coupled electron transfer. Chem. Rev. 107, 5004–5064 (2007)

    Article  CAS  Google Scholar 

  49. Y. Mizutani, Y. Uesugi, T. Kitagawa, Intramolecular vibrational energy redistribution and intermolecular energy transfer in the (d, d) excited state of nickel octaethylporphyrin. J. Chem. Phys. 111, 8950–8961 (1999)

    Article  CAS  Google Scholar 

  50. D. Meisel, G. Czapski, One-electron transfer equilibriums and redox potentials of radicals studied by pulse radiolysis. J. Phys. Chem. 79, 1503–1509 (1975)

    Article  CAS  Google Scholar 

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Acknowledgments

This work was partially supported by a Grant-in-Aid for Scientific Research on Innovative Areas of “Coordination Programming” (no. 22108523) and “Molecular Activation” (no. 23105537), a Grant-in-Aid for Scientific Research (A) (no. 21245016), a Grant-in-Aid for Scientific Research (B) (no. 20350029), a Grant-in-Aid for JSPS Fellow, and the Global COE Program, “Science for Future Molecular Systems”, from the Ministry of Education, Culture, Sports, Science and Technology of Japan. M.A. also thanks Tokuyama Science Foundation for financial support.

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  1. Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka, 819-0395, Japan

    Toru Okawara, Masaaki Abe, Hisashi Shimakoshi & Yoshio Hisaeda

  2. International Research Center for Molecular Systems (IRCMS), Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka, 819-0395, Japan

    Yoshio Hisaeda

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  1. Toru Okawara
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Correspondence to Masaaki Abe or Yoshio Hisaeda.

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Okawara, T., Abe, M., Shimakoshi, H. et al. A Pd(II)-hydroxyporphycene: synthesis, characterization, and photoinduced proton-coupled electron transfer. Res Chem Intermed 39, 161–176 (2013). https://doi.org/10.1007/s11164-012-0640-8

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