Chiroptical and Computational Studies of a Bridled Chiroporphyrin and of Its Nickel(II), Copper(II), and Zinc(II) Complexes.
Circular dichroism (CD) spectra and density functional theory (DFT) calculations are reported for a series of conformationally bistable chiroporphyrins with 8-methylene bridles MBCP-8, which can display either an αααα or an αβαβ orientation of their meso substituents. From DFT geometry optimizations...
| Publicado en: | Journal of the American Chemical Society Vol. 128; no. 19; pp. 6347 - 6357 |
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| Autores principales: | , , , , , , |
| Formato: | Artículo |
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American Chemical Society
5/17/2006
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=20956539&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 20956539 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 5/17/2006 vid: 128 iid: 19 pid: 997 pub: American Chemical Society artinfo: ui: 20956539 10.1021/ja054926o ppf: 6347 ppct: 10 formats: tig: atl: Chiroptical and Computational Studies of a Bridled Chiroporphyrin and of Its Nickel(II), Copper(II), and Zinc(II) Complexes. aug: au: Maheut, Geraldine Castaings, Anna Pëcaut, Jacques Daku, Latévi Max Lawson Pesciteili, Gennaro Di Bari, Lorenzo Marchon, Jean-Claude affil: Département de Recherche Fondamentale sur la Matiëre Condensée, CEA-Grenoble Département Integration Héterogene Silicium, Leti, CEA-Grenoble Université de Genëve Dipartimento di Chimica e Chimica industriale, CNR-ICCOM, Via Risorgimento 35, 1-56126 Pisa, Italy su: Circular dichroism Density functionals Nickel compounds Copper compounds Zinc compounds Carbenes sug: subj: Circular dichroism Density functionals Nickel compounds Copper compounds Zinc compounds Carbenes ab: Circular dichroism (CD) spectra and density functional theory (DFT) calculations are reported for a series of conformationally bistable chiroporphyrins with 8-methylene bridles MBCP-8, which can display either an αααα or an αβαβ orientation of their meso substituents. From DFT geometry optimizations, the most stable form of ZnBCP-8 is found to be the αααα conformer. By passing to NiBCP-8, there is a strong stabilization of the αβαβ conformation with respect to the αααα conformation, consistent with the X-ray structures of αααα-ZnBCP-8 and αβαβ-NiBCP-8. A correlation between the sign of the CD signal in the Soret region and the conformation of the BCP-8 compounds is reported: the αααα conformers HBCP-8 and ZnBCP-8 show a positive CD signal, whereas the αβαβ conformers NiBCP-8 and CuBCP-8 exhibit a negative signal. The possible contributions to the rotational strengths of αβαβ-NiBCP-8 and αααα-ZnBCP-8, calculated on the basis of their crystal structures, have been analyzed. The CD signals are found to result from a combination of both the inherent chirality of the porphyrin and of extrinsic contributions due to the chiral bridles. These results may have a broad significance for understanding the chiroptical properties of chiral porphyrins and hemoproteins and for monitoring stimuli-responsive, conformationally bistable chiroporphyrin compounds. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2006 holdings: @attributes: islocal: N |
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