Light-harvesting macroring accommodating a tetrapodal ligand based on complementary and cooperative coordinations.
A porphyrin macroring, mimicking the light-harvesting complex of photosynthetic purple bacteria, was synthesized by self-assembling trisporphyrinatoZn(II) complexes with imidazolyl substituents at both molecular terminals. Very strong complementary coordination of imidazolyl to Zn(II) afforded exclusively the cyclic trimer of trisporphyrin under dilute conditions at 27 degrees C in CHCl3/MeOH = 9/1 (v/v). 1H NMR spectra of the macroring indicate the existence of two topological isomers, one symmetric and one asymmetric. Use of three noncoordinated porphyrinatoZn(II) sites allows a tetrapodal ligand to be incorporated into the cavity of the macroring. A Job plot and the clear bending behavior on UV-vis titration indicated the formation a 1:1 complex; the heterogeneity of two topological isomers was not observed, and both isomers similarly accommodated the tetrapodal ligand. The association constant obtained by curve fitting analysis was 8 x 108 M-1 in toluene. This large association constant reflects the cooperative nature of three coordination sites.
Kuramochi
Yusuke
Y
Graduate School of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, Nara 630-0192, Japan.
Satake
Akiharu
A
Kobuke
Yoshiaki
Y
D008024:Ligands; D045342:Light-Harvesting Protein Complexes / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis*; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
D008024:Ligands; D045342:Light-Harvesting Protein Complexes; D009942:Organometallic Compounds; D011166:Porphyrins; C492096:self-assembled cyclic trisporphyrin trimer; C492095:trisporphyrin; D015032:Zinc