The electronic effect in supramolecular self-assembly of <Emphasis Type="Italic">para-</Emphasis>substituted tetraphenylporphyrinatozinc(II) with imidazolyl-linked porphyrinatomanganese(III) by coordinative bonding |
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Authors: | Jin-Wang Huang Chun-Hua Dong Jia-Zheng Lu Han-Cheng Yu Bo Fu Liang-Nian Ji |
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Institution: | (1) State Key Laboratory of Optoelectronic Material and Technologies & School of Chemistry and Chemical Engineering, Sun Yat-Sen University, 510275 Guangzhou, China |
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Abstract: | The supramolecular self-assembly of para-substituted tetraphenylporphyrin complexes of zinc(II), Zn(p-X)TPP, with imidazolyl-linked porphyrinatomanganese(III), Mn(p-lmBPTPP)Cl, driven by coordinative bonding has been investigated by fluorescence spectra, electrospray mass spectrometry, 1H-n.m.r. and u.v.–vis. spectra. The association constants of the supramolecular complexes, Kc, were calculated using fluorescence spectroscopic titration data at suitable dilute concentration ranges in which the fluorescent quenching of Zn(p-X)TPP by Mn(p-ImBPTPP)Cl is a static process. The electronic effect in the supramolecular self-assembly of para-substituted . porphyrinatozinc(II) with imidazolyl-linked porphyrinatomanganese(III) is discussed. The non-linear dependence of log Kc on the Hammett constants was found, which suggested that the electronic effect in para-substituents of tetraphenylporphyrin complexes of zinc(II) is an important, but not a sole factor effecting the association constants of the Zn(p-X)TPP–Mn(p-ImBPTPP)Cl supramolecular complexes. The results indicate that the closed conformation of the Zn(p-X)TPP–Mn(p-ImBPTPP)Cl supramolecular complex is another important factor effecting the association constants of the Zn(p-X)TPP–Mn(p-ImBPTPP)Cl supramolecular complexes. |
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