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Photosynthetic Reaction Center Mimicry: Low Reorganization Energy Driven Charge Stabilization in Self-Assembled Cofacial Zinc Phthalocyanine Dimer-Fullerene Conjugate

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 131, Issue 25, Pages 8787-8797

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/ja903467w

Keywords

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Funding

  1. National Science Foundation [CHE 0804015]
  2. KOSEF/MEST [R31-2008-000-10010-0]
  3. Global COE program
  4. Ministry of Education, Culture, Sports, Science and Technology, Japan
  5. [19205019]
  6. [19750034]
  7. National Research Foundation of Korea [R31-2008-000-10010-0] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
  8. Division Of Chemistry
  9. Direct For Mathematical & Physical Scien [804015] Funding Source: National Science Foundation

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By employing well-defined self-assembly methods, a biomimetic bacterial photosynthetic reaction center complex has been constructed, and photoinduced electron transfer originating in this supramolecular donor-acceptor conjugate has been investigated. The biomimetic model of the bacterial special pair donor, a cofacial zinc phthalocyanine dimer, was formed via potassium ion induced dimerization of 4,5,4',5',4 '', 5 '',4''',5'''-zinc tetrakis(1,4,7,10,13-pentaoxatridecamethylene)phthalocyanine. The dimer was subsequently self-assembled with functionalized fullerenes via two-point binding involving axial coordination and crown ether-alkyl ammonium cation complexation to form the donor-acceptor pair, mimicking the noncovalently bound entities of the bacterial photosynthetic reaction center. The adopted self-assembly methodology yielded a supramolecular complex of higher stability with defined geometry and orientation as revealed by the binding constant and computational optimized structure. Unlike the previously reported porphyrin analog, the present phthalocyanine macrocycle based model system exhibited superior electron-transfer properties including formation of a long-lived charge-separated state, a key step of the photosynthetic light energy conversion process. Detailed analysis of the kinetic data in light of the Marcus theory of electron transfer revealed that small reorganization energy of the relatively rigid phthalocyanine is primarily responsible for slower charge-recombination process. The importance of the cofacial dimer in stabilizing the charge-separated state is borne out in the present all-supramolecular reaction center donor-acceptor mimic.

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