Tuning the photophysical and redox properties of metallocorroles by iodination
Jenya Vestfrid1, Israel Goldberg, Zeev Gross
1Schulich Faculty of Chemistry, Technion - Israel Institute of Technology , Haifa 32000, Israel.
Abstract:
Facile procedures were developed for selective iodination of aluminum and gallium corroles; crystallographic characterization shows that the main structural aspects are not changed (the macrocycle remains planar). Absorption maxima are red-shifted by 3-5 nm/iodine, singlet lifetimes are reduced to <80 ps, and emissions from long-lived excited states come into effect. The iodinated corroles display prompt fluorescence, phosphorescence, and delayed thermal fluorescence, all at room temperature. The effect on redox potentials appears to be additive for each additional iodine and, surprisingly, is practically identical to that of the other three halides. The conclusions of this work are of large importance for the design of metallocorroles that are best suited for the various applications where metallocorroles are used as catalysts and photosensitizers.
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Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly,...
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