Photosynthesis Research

, Volume 95, Issue 2–3, pp 363–371 | Cite as

Mimicking the photosynthetic system with strong hydrogen bonds to promote proton electron concerted reactions

  • Isamu Kinoshita
  • Hideki Hashimoto
  • Takanori Nishioka
  • Riichi Miyamoto
  • Naoto Kuwamura
  • Yuki Yoshida
Regular Paper


A Copper(2+) complex with a CuII–C bond containing sp3 configuration was used to investigate the role of strong hydrogen bonds in proton coupled electron transfer (PCET) reactions. The only example of a CuII–C system realized so far is that using tris-(pyridylthio)methyl (tptm) as a tetradentate tripodal ligand. Using this ligand, [CuF(tptm)] and [Cu(tptm)(OH)] have been prepared. The former complex forms supra-molecular arrays of layers of the complex between which hydroquinone is intercalated in the crystalline phase. This hydroquinone intercalation crystal was prepared via the photochemical conversion of quinone during the crystallization process. This conversion reaction probably involves a proton coupled electron transfer process. The nuclear magnetic resonance spectroscopic analysis of the reaction mixture shows the presence of Cu(III) during the conversion reaction. These results strongly suggest the presence of the molecular aggregate of the [CuF(tptm)] complex, water and quinone in the solution phase during the quinone to hydroquinone conversion. The presence of this type of aggregate requires a strong hydrogen bond between the [CuF(tptm)] complex and water. The presence of this particular hydrogen bond is a unique character of such a complex that has the CuII–C bond. This complex is used as a model for photosynthetic water splitting since the photoconversion of quinone to hydroquinone also involves the production of oxygen from water.


Proton coupled electron transfer Quinone hydroquinone conversion Copper complex 



Proton coupled electron transfer












Normal hydrogen electrode


  1. Burla MC, Camalli M, Carrozzini B, Cascarano GL, Giacovazzo C, Polidori G, Spagna R (2003) SIR2002 Google Scholar
  2. Diner BA, Babcock GT (1996) Oxygen Photosynthesis; The Light Reactions. In: Ort DR, Yocum CF (eds) Kluwer Academic Publishers, Netherlands: pp 213–247Google Scholar
  3. Ferreira KN, Iverson TM, Maghlaoui K, Barber J, Iwata S (2004) Architecture of the Photosynthetic Oxygen-Evolving Center. Science 303:1831–1838PubMedCrossRefGoogle Scholar
  4. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA, Vreven T Jr, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2003) Gaussian 03, Revision B.03. Gaussian Inc. Pittsburgh PAGoogle Scholar
  5. Hays AA, Vassiliev IR, Golbeck JH, Debus RJ (1998) Role of D1-His190 in Proton-Coupled Electron Transfer Reactions in Photosystem II: A chemical Complementation Study. Biochemistry 37:11352–11365PubMedCrossRefGoogle Scholar
  6. Kinoshita I, Wright LJ, Kubo S, Kimura K, Sakata A, Yano T, Miyamoto R, Nishioka T, Isobe K (2003) Design and Synthesis of Copper Complexes of Novel Ligands based on the Pyridinethiol Group. J Chem Soc Dalton Trans: 1993–2003Google Scholar
  7. Mamedov F, Sayre RT, Styring S (1998) Involvement of Histidine 190 on the D1 Protein in Electron/Proton Transfer Reactions on the Donor Side of Photosystem II. Biochemistry 37:14245–14256PubMedCrossRefGoogle Scholar
  8. Miyamoto R, Hamazawa RT, Hirotsu M, Nishioka T, Kinoshita I, Wright LJ (2005) A two-dimensional clathrate hydrate sandwiched by planar arrays of a copper complex. Chem Commun 32:4047–4049CrossRefGoogle Scholar
  9. Miyamoto R, Santo R, Matsushita T, Nishioka T, Ichimura A, Teki Y, Kinoshita I (2005) A complete series of copper(ii) halide complexes (X = F, Cl, Br, I) with a novel Cuii–C(sp3) bond. Dalton Trans 19:3179–3186PubMedCrossRefGoogle Scholar
  10. Pflugrath JW (1999) CrystalClear. Rigaku Corporation 1999, CrystalClear Software User’s Guide. Molecular Structure Corporation ©2000. Acta Cryst D 55:1718–1725CrossRefGoogle Scholar
  11. Rigaku and Rigaku/MSC (2000–2004) CrystalStructure 3.6.0. Crystal structure analysis package, 9009 New Trails Dr. The Woodlands TX 77381 USAGoogle Scholar
  12. Russo TV, Martin RL, Hay PJ (1995) Effective Core Potentials for DFT Calculations. J Phys Chem 99:17085–17087CrossRefGoogle Scholar
  13. Santo R, Miyamoto R, Tanaka R, Nishioka T; Sato K, Toyota K, Obata M, Yano S, Kinoshita I, Ichimura A, Takui T (2006) Diamagnetic-paramagnetic conversion of tris(2-pyridylthio)methylcopper(III) through a structural change from trigonal bipyramidal to octahedral. Angew Chem Int Ed 45:7611–7614CrossRefGoogle Scholar
  14. Scudder M, Dance I (2002) Dimorphic Intra- and Intermolecular Aryl Motifs in Symmetrical Hexafaceted Molecules (ArnX)3Y-Z-Y(XArn)3. Chem Eur J 8:5456–5468Google Scholar
  15. Sheldrick GM (1997) SHELX97, Program for crystal structure refinement. University of Gottingen, Gottingen, GermanyGoogle Scholar
  16. Shliver DF (1969) The Manipulation of Air-sensitive Compounds, McGraw-HillGoogle Scholar
  17. Sjodin M, Irebo T, Utas JE, Lind J, Merenyi G, Akermark B, Hammarstrom L (2006) Kinetic Effects of Hydrogen Bonds on Proton-Coupled Electron Transfer from Phenols. J Am Chem Soc 128:13076–13083PubMedCrossRefGoogle Scholar
  18. teXsan : Crystal Structure Analysis package (1985) and (1999) Molecular Structure Corporation, San Diego, CAGoogle Scholar
  19. Van Bolhuis F, Kiers CT (1978) Refinement of the crystal structure of p-benzoquinone at −160°C. Acta Crystallogr Sect B 34:1015–1016CrossRefGoogle Scholar
  20. Watkin DJ, Prout CK, Carruthers JR, Betteridge PW (1996) CRYSTALS Issue 10. Chemical Crystallography Laboratory, Oxford, UKGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2007

Authors and Affiliations

  • Isamu Kinoshita
    • 1
  • Hideki Hashimoto
    • 1
  • Takanori Nishioka
    • 1
  • Riichi Miyamoto
    • 1
  • Naoto Kuwamura
    • 1
  • Yuki Yoshida
    • 1
  1. 1.Graduate School of ScienceOsaka-City UniversityOsakaJapan

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