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Enthalpy-entropy compensation upon syn-anti conformational switching of bis-porphyrins by amines and alcohols

Victor V. Borovkov

Entropy Control Project, ICORP, JST, 4-6-3 Kamishinden, Toyonaka-shi, Osaka 560-0085, Japan

Corresponding author.

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Guy A. Hembury

Entropy Control Project, ICORP, JST, 4-6-3 Kamishinden, Toyonaka-shi, Osaka 560-0085, Japan

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Yoshihisa Inoue

Entropy Control Project, ICORP, JST, 4-6-3 Kamishinden, Toyonaka-shi, Osaka 560-0085, Japan

Corresponding author.

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https://doi.org/10.1142/S1088424603000434Cited by:5 (Source: Crossref)

Abstract

Upon interaction with amine and alcohol guests, Zn-Zn and Zn-2H ethane-bridged bis-porphyrin hosts undergo dramatic conformational switching from a syn to an anti form. The thermodynamic parameters obtained exhibit excellent linear enthalpy-entropy correlations, which are distinctly different for amines and alcohols but essentially independent of the host structure. Analyses of the compensation plots reveal a more rigid complex structure and more extensive desolvation upon complexation with amines than for alcohols, which may be ascribed to the different nucleophilicity, binding strength, solvation and geometry.

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