structural and molecular characterization of meso-substituted zinc porphyrins a dft supported study结构和分子特征meso-substituted锌卟啉dft支持研究.pdfVIP

Molecules 2011, 16, 9957-9971; doi:10.3390/molecule OPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Structural and Molecular Characterization of meso-Substituted Zinc Porphyrins: A DFT Supported Study Rudolf Słota 1,*, Małgorzata A. Broda 1, Gabriela Dyrda 1, Krzysztof Ejsmont 1 and 2 Giuseppe Mele 1 Faculty of Chemistry, Opole University, ul. Oleska 48, 45-052 Opole, Poland 2 Department of Engineering and Innovation, University of Salento, Via Arnesano, 73100 Lecce, Italy * Author to whom correspondence should be addressed; E-Mail: rslota@uni.opole.pl; Tel.: +48-77-452-7131; Fax: +48-77-452-7101. Received: 2 November 2011; in revised form: 22 November 2011 / Accepted: 22 November 2011 / Published: 1 December 2011 Abstract: Structural parameters of a range of over 100 meso-substituted zinc porphyrins were reviewed and compared to show how far the nature of the functional group may affect the interatomic distances and bond angles within the porphyrin core. It was proved that even despite evident deformations of the molecular structure, involving twisting of the porphyrins central plane, the coupled π-bonding system remains flexible and stable. DFT calculations were applied to a number of selected porphyrins representative for the reviewed compounds to emphasize the relevance of theoretical methods in structural investigations of complex macrocyclic molecular systems. Experimental and DFT-simu