Abstract
The Soret absorption spectra of six synthetic rigid porphyrin dimers whose crystal structures have been determined are simulated using simple exciton theory. The objective is to test the validity of the point dipole and associated approximations; the electronic interaction parameters are thus calculated using data obtained from the monomer spectra, with no adjustable parameters. Satisfactory agreement between theory and experiment is obtained for one class of dimers but not for a second. This poses a challenge for semiempirical electronic structure methods as to whether improvements over the point dipole calculations can be obtained.
Similar content being viewed by others
References
Allen JP, Feher G, Yeates TO, Komiya H and Rees DC (1987) Structure of the reaction center from Rhodobacter sphaeroides R-26: The cofactors. Proc Natl Acad Sci. USA 84: 5730–5734
Bixon M, Jortner J, Michel-Beyerle ME, Orgodnik A and Lersch W (1987) The role of the accessory bacteriochlorophyll in the reaction centers of photosynthetic bacteria: Intermediate acceptor in the primary electron transfer? Chem Phys Lett 140: 626–630
Breton J, Martin J-L, Migus A, Antonetti A and Orszag A (1986) Femtosecond spectroscopy of excitation energy transfer and initial charge separation in the reaction center of the photosynthetic bacterium Rhodopseudomonas viridis. Proc Natl Acad Sci USA 83: 5121–5125
Chang C-H, Tiede DM, Tang J, Smith U, Norris JR and Schiffer M (1986) Structure of Rhodopseudomonas sphaeroides R-26 reaction center. FEBS Lett 205: 82–86
Deisenhofer J, Epp O, Miki K, Huber R and Michel H (1984) X-ray structure analysis of a membrane protein complex: Electron density map at 3 Å resolution and a model of the chromophores of the photosynthetic reaction center from Rhodopseudomonas viridis. J Mol Biol 180: 385–398
Deisenhofer J, Epp O, Miki K, Huber R and Michel H (1985) Structure of the protein subunits in the photosynthetic reaction center of Rhodopseudomonas viridis at 3 Å resolution. Nature 318: 618–624
Eccles J, Honig B and Schulten K (1988) Spectroscopic determinants in the reaction center of Rhodopseudomonas viridis. Biophys J 53: 137–144
Fischer SF and Scherer POJ (1987) On the early charge separation and recombination processes in bacterial reaction centers. Chemical Physics 115: 151–158
Hanson LK, Fajer J and Thompson M (1987a) Environmental effects on the properties of chlorophylls in vivo. Theoretical models. In: Biggins J (ed) Progress in Photosynthesis Research Vol I, pp 311–331. Dordrecht: Martinus Nijhoff
Hanson LK, Fajer J, Thompson MA and Zerner M (1987b) Electrochromic effects of charge separation in bacterial photosynthesis: Theoretical models. J Am Chem Soc 109: 4728–4730
Hanson LK, Thompson MA, Zerner MC and Fajer J (1988a) Theoretical models of electrochromic and environmental effects on bacterio-chlorophylls and -pheophytins in reaction centers. In: Breton J and Vermèglio A (eds) Photosynthetic Bacterial Reaction Center: Structure and Dynamics, NATO ASI Series, Series A: Life Sciences Vol 149, pp 355–367. New York: Plenum
Hanson LK (1988b) Theoretical calculations of photosynthetic pigments. Photochem Photobiol 47: 903–921
Heiler D, McLendon G, Rogalskyj P (1987) Synthesis and electron-transfer rates of coplanar diporphyrins: Models for (heme) protein-protein electron transfer reactions. J Am Chem Soc 109: 604–606
Martin J-L, Breton J, Hoff AJ, Migus A and Antonetti A (1986) Femtosecond spectroscopy of electron transfer in the reaction center of photosynthetic bacterium Rhodopseudomonas sphaeroides R-26: Direct electron transfer from the dimeric bacteriochlorophyll primary donor to the bacteriopheophytin acceptor with a time constant of 2.8±0.2 psec. Proc Natl Acad Sci USA 83: 957–961
Michel-Beyerle ME, Plato M, Deisenhofer J, Michel H, Bixon M and Jortner J (1988) Unidirectionality of charge separation in reaction centers of photosynthetic bacteria. Biochim Biophys Acta 932: 52–70
Ogrodnik A, Remy-Richter N, Michel-Beyerle ME and Feick R (1987) Observation of activationless recombination in reaction centers of R. sphaeroides. A new key to the primary electron-transfer mechanism. Chem Phys Lett 135: 576–581
Osuka A and Maruyama K (1987) A twisted and partially overlapping porphyrin dimer as a new model of special pair in photosynthetic reaction center. Chem Lett: 825–828
Osuka A and Maruyama K (1988) Synthesis of naphthalenebridged porphyrin dimers and their orientation dependent exciton coupling. J Am Chem Soc 110: 4454–4456
Parson WW and Warshel A (1987) The spectroscopic properties of photosynthetic reaction centers II. Application of the theory to Rhodopseudomonas viridis. J Am Chem Soc 109: 6152–6163
Plato M, Tränkle E, Lubitz W, Lendzian F and Möbius K (1986) Molecular orbital investigation of dimer formations of bacteriochlorophyll a. Model configurations for the primary donor of photosynthesis. Chemical Physics 107: 185–196
Plato M and Winscom CJ (1988) A configuration interaction (CI) description of vectorial electron transfer in bacterial reaction centers. In: Breton J and Vermèglio A (eds) Photosynthetic Bacterial Reaction Center: Structure and Dynamics, NATO ASI Series, Series A: Life Sciences Vol 149, pp 421–424. New York: Plenum
Sessler JL, Johnson MR and Hugdahl J (1986) Stereoselective synthesis of β,γ-unsaturated esters and lactones. Applications to pyrenophorol synthesis. J Org Chem 51: 2838–2840
Sessler JL and Johnson MR (1987) The synthesis of 1,2- and 1,4-phenylene-linked bisquinone-substituted porphyrin dimers. Angew Chem Int Ed Engl 26: 678–680
Sessler JL, Johnson MR, Lin T-Y and Creager SE (1988) Quinone-substituted monometalated porphyrin dimers: Models for photoinduced charge separation at fixed orientation and energy. J Am Chem Soc 110: 3659–3661
Sessler JL, Johnson MR and Lin T-Y (1989a) Absorption and static emission properties of monometalated quinone-substituted porphyrin dimers: Evidence for “superexchange” mediated electron transfer in multicomponent photosynthetic model systems. Tetrahedron: in press
Sessler JL, Rodriguez J, Kirmaier C, Johnson MR, Creager SE and Holten D (1989b) J Am Chem Soc: to be submitted
Sessler JL, Johnson MR, Creager SE, Fettinger J, Ibers JA, Rodriguez J, Kirmaier C and Holten D (1989c) Quinone substituted porphyrin dimers: New photosynthetic model systems. Proceedings of the 10th International Congress on Photobiology, Jerusalem, Israel, in press
Sessler JL, Johnson MR, Ibers JA and Fettinger J (1989d) J Am Chem Soc: to be submitted
Tabushi I and Sasaki T (1982) Gable-porphyrin as a cytochrome-c3 model. Tetrahedron Lett 23: 1913–1916
Tabushi I, Kugimiya S-I, Kinnaird MG and Sasaki T (1985) Artificial allosteric system. 2. Cooperative 1-methylimidazole binding to an artificial allosteric system, zinc-gable porphyrin-dipyridylmethane complex. J Am Chem Soc 107: 4192–4199
Wasielewski MR (1988) Synthetic models for photosynthesis. Photochem Photobiol 47: 923–929
Warshel A and Parson WW (1987) The spectroscopic properties of photosynthetic reaction centers. I. Theory. J Am Chem Soc 109: 6143–6152
Won Y and Friesner RA (1988a) Simulation of optical spectra from the reaction center of Rhodopseudomonas viridis. J Phys Chem 92: 2208–2214
Won Y and Friesner RA (1988b) On the viability of the superexchange mechanism in the primary charge separation step of bacterial photosynthesis. Biochim Biophys Acta 935: 9–18
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Won, Y., Friesner, R.A., Johnson, M.R. et al. Exciton interactions in synthetic porphyrin dimers. Photosynth Res 22, 201–210 (1989). https://doi.org/10.1007/BF00048299
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00048299