Energy transfer followed by electron transfer in a supramolecular triad composed of boron dipyrrin, zinc porphyrin, and fullerene: a model for the photosynthetic antenna-reaction center complex.
The first example of a working model of the photosynthetic antenna-reaction center complex, constructed via self-assembled supramolecular methodology, is reported. For this, a supramolecular triad is assembled by axially coordinating imidazole-appended fulleropyrrolidine to the zinc center of a covalently linked zinc porphyrin-boron dipyrrin dyad. Selective excitation of the boron dipyrrin moiety in the boron dipyrrin-zinc porphyrin dyad resulted in efficient energy transfer (k(ENT)(singlet) = 9.2 x 10(9) s(-)(1); Phi(ENT)(singlet) = 0.83) creating singlet excited zinc porphyrin. Upon forming the supramolecular triad, the excited zinc porphyrin resulted in efficient electron transfer to the coordinated fullerenes, resulting in a charge-separated state (k(cs)(singlet) = 4.7 x 10(9) s(-)(1); Phi(CS)(singlet) = 0.9). The observed energy transfer followed by electron transfer in the present supramolecular triad mimics the events of natural photosynthesis. Here, the boron dipyrrin acts as antenna chlorophyll that absorbs light energy and transports spatially to the photosynthetic reaction center, while the electron transfer from the excited zinc porphyrin to fullerene mimics the primary events of the reaction center where conversion of the electronic excitation energy to chemical energy in the form of charge separation takes place. The important feature of the present model system is its relative "simplicity" because of the utilized supramolecular approach to mimic rather complex "combined antenna-reaction center" events of photosynthesis.
D'Souza
Francis
F
Department of Chemistry, Wichita State University, 1845 Fairmount, Wichita, Kansas 67260-0051, USA. francis.dsouza@wichita.edu
Smith
Phillip M
PM
Zandler
Melvin E
ME
McCarty
Amy L
AL
Itou
Mitsunari
M
Araki
Yasuyuki
Y
Ito
Osamu
O
D000632:Aminopyrine / Q000737:chemistry*; D001895:Boron / Q000737:chemistry*; D004579:Electron Transport; D004735:Energy Transfer / Q000528:radiation effects*; D004736:Energy-Generating Resources; D037741:Fullerenes / Q000737:chemistry*; D008665:Metalloporphyrins / Q000737:chemistry; D008954:Models, Biological; D010788:Photosynthesis; D013057:Spectrum Analysis; D015032:Zinc / Q000737:chemistry*
D037741:Fullerenes; D008665:Metalloporphyrins; D000632:Aminopyrine; D015032:Zinc; D001895:Boron