Conformational and Electronic Effects of Phenyl-Ring Fluorination on the Photophysical Properties of Nonplanar Dodecaarylporphyrins
| Autor: | Daniel J. Nurco, and Kevin M. Smith, Vladimir S. Chirvony, Jennifer L. Retsek, Craig J. Medforth, Steve Gentemann, Dewey Holten |
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| Rok vydání: | 2001 |
| Předmět: | |
| Zdroj: | The Journal of Physical Chemistry B. 105:6396-6411 |
| ISSN: | 1520-5207 1520-6106 |
| DOI: | 10.1021/jp004556k |
| Popis: | Static and time-resolved optical measurements have been performed on a number of free-base and zinc dodecaarylporphyrins with varying degrees of fluorination of the peripheral aryl rings. These studies were performed in a variety of solvents of differing polarity and metal-ligating ability and at room and low temperatures. All of the compounds are deduced to be nonplanar based on their perturbed photophysical properties relative to planar analogues and on the X-ray data available for these molecules. The dodecaarylporphyrins studied generally separate into two classes based on their photophysical properties and the presence or absence of meso-pentafluorophenyl rings. The photophysical properties are clearly affected by the electron-withdrawing characteristics of these fluorinated phenyl rings, but structural effects derived from the interaction of the phenyl rings with each other, the macrocycle, and the solvent are also apparent. Many of the differences in properties among the molecules studied and the p... |
| Databáze: | OpenAIRE |
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