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Non-Covalent Multi-Porphyrin Assemblies by Imenne Bouamaied, Timur Coskun, Eugen Stulz (auth.), Enzo

By Imenne Bouamaied, Timur Coskun, Eugen Stulz (auth.), Enzo Alessio (eds.)

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"This ebook offers an outline of the synthesis, constitution, and homes of molecules bought by way of connecting a number of porphyrins or metalloporphyrins via quite a few chemical linkages. This handsomely produced booklet offers the reader a large advent to this renowned and significant box. a lot of the paintings encompassed during this zone is galvanized through the will to acquire photochemically responsive molecules in a position to mimicking a variety of features of photosynthesis… As with many edited volumes of this sort, there's a specific amount of replica insurance of a few issues. additionally the point of interest is essentially at the equipment used to generate the multiporphyrin arrays, and every so often much less consciousness is given to the houses, except the structural houses of those arrays. This e-book might be instructed to readers attracted to an up to date evaluate of the multiporphyrin arrays already synthesized, only if those readers have entry to a well-funded library." (Alan L. Balch, magazine of the yankee Chemical Society, Vol. 129 (17), 2007)

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These examples demonstrate in an elegant way that multiporphyrin arrays do not only serve to model the photosynthetic reaction center, but highly active catalysts can be designed and synthesized. Here, the axial coordination chemistry to porphyrins is not used to arrange the porphyrins in a specific way, but rather the porphyrins serve to form an active catalyst via geometry stabilization of the ligated metal complex. A porphyrin calixarene conjugate 23 was also self-assembled using DABCO as a ligand to the zinc metallated porphyrins [49].

Norsten TB, Branda NR (2001) Adv Mater 13:347 9. Samachetty HD, Branda NR (2005) Chem Commun 22:2840 10. D’Souza F, Smith PM, Gadde S, McCarty AL, Kullman MJ, Zandler ME, Itou M, Araki Y, Ito O (2004) J Phys Chem B 108:11333 11. D’Souza F, El-Khouly ME, Gadde S, McCarty AL, Karr PA, Zandler ME, Araki Y, Ito O (2005) J Phys Chem B 109:10107 12. D’Souza F, Deviprasad GR, Zandler ME, El-Khouly ME, Fujitsuka M, Ito O (2003) J Phys Chem A 107:4801 13. D’Souza F, Chitta R, Gadde S, Zandler ME, McCarty AL, Sandanayaka ASD, Araki Y, Ito O (2005) Chem-Eur J 11:4416 14.

The parasubstituted bisporphyrin cannot adopt the cofacial conformation required for this type of complex and forms a higher-order 2 : 2 intermolecular assembly, which is stable over a wide range of DABCO concentrations. Molecular modelling revealed the energetic reasons for this behavior. The modelled intramolecular complex of DABCO with the para-isomer is 54 kJ mol–1 less stable than the meta-isomer, because a cofacial arrangement of the porphyrin units can only be achieved by distorting the planarity of the amide groups.

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