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- W2088565563 endingPage "5550" @default.
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- W2088565563 abstract "A series of cerium(IV) bis-porphyrinate double-deckers [Ce(bbpp)(2)] (BBPP=5,15-bis(4-butoxyphenyl)porphyrin dianion), [Ce(tmpp)(2)] (TMPP=5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin dianion), [Ce(tfpp)(2)] (TFPP=5,10,15,20-tetrakis(4-fluorophenyl)porphyrin dianion), [Ce(tmcpp)(2)] (TMCPP=5,10,15,20-tetrakis(4-methoxycarbonylphenyl)porphyrin dianion), and [Ce(tmpp)(tmcpp)] was prepared. They bind three Ag(+) ions to their concave porphyrin pi subunits (pi-clefts) according to a positive homotropic allosteric mechanism with Hill coefficients (n(H)) of 1.7-2.7. The rotation rates of the porphyrin ligands in [Ce(bbpp)(2)] were evaluated to be 200 s(-1) at 20 degrees C (DeltaG$rm{^{ne }_{293}}$=14.1 kcal mol(-1)) and 220 s(-1) at -40 degrees C (DeltaG$rm{^{ne }_{233}}$=11.0 kcal mol(-1)) without and with Ag(+) ions, respectively. These results consistently support our unexpected finding that Ag(+) binding can accelerate rotation of the porphyrin ligand. On the basis of UV-visible, (1)H NMR, and resonance Raman spectral measurements, the rate enhancement of the rotational speed of the porphyrin ligands is attributed to conformational changes of the porphyrin in cerium(IV) bis-porphyrinate induced by binding of Ag(+) guest ions in the clefts. This novel concept of positive homotropic allosterism is applicable to the molecular design of various supramolecular and switch-functionalized systems." @default.
- W2088565563 created "2016-06-24" @default.
- W2088565563 creator A5053113130 @default.
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- W2088565563 creator A5085172968 @default.
- W2088565563 date "2002-12-16" @default.
- W2088565563 modified "2023-10-18" @default.
- W2088565563 title "Allosteric Binding of an Ag+ Ion to Cerium(IV) Bis-porphyrinates Enhances the Rotational Activity of Porphyrin Ligands" @default.
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