| Autor: |
Chaudhri, Nivedita, Guberman-Pfeffer, Matthew J., Zeller, Matthias, Brückner, Christian |
| Předmět: |
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| Zdroj: |
Dalton Transactions: An International Journal of Inorganic Chemistry; 8/21/2024, Vol. 53 Issue 31, p13142-13150, 9p |
| Abstrakt: |
Nominally, meso-hydroxyoxochlorins, like known 5-hydroxy-7-oxo-octaethylchlorin (9), its nickel complex [5-hydroxy-7-oxo-octaethylchlorinato]nickel(II) (9Ni), or the novel 5-hydroxy-7,17-dioxo-octaethylbacteriochlorin (10), incorporate an acetylacetonate (acac)-moiety in the enol form in their chromophore structures. X-Ray diffraction studies of the compounds show the presence of a strong H-bond between the enol and flanking β-ketone. Like acac, the functionality can be deprotonated. However, unlike regular acac-like moieties, we did not find any indication that this functionality is competent in chelating any of the 3d or 4d transition metal ions tested. Evidently, the conjugation that contributes to the stability of acac as a ligand cannot be expressed in the meso-hydroxyoxochlorins since it would perturb the aromaticity of the porphyrinic chromophores; in other words, the metal binding energies do not offset the loss in aromaticity. The halochromic properties of the molecules provide some more insight into the location of the protonation/deprotonation sites. The interpretation of the findings is supported by computations. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
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