This chapter discusses self-assembly of porphyrin arrays. Porphyrins represent ideal building blocks for the synthesis of oligomeric and polymeric arrays through the self-assembly technique. They are rigid, can easily be functionalized, and a number of different metals can be inserted in the center of the macrocycle. The central metal of the porphyrin is coordinated to four nitrogens and can accept either one or two additional apical donor atoms to give a square pyramidal or octahedral coordination sphere respectively. A number of self-assembled porphyrin arrays have been reported, held together by either hydrogen-bonding or metal–ligand coordination interactions. The chapter focuses on coordination oligomers where the key oligomerization interactions involve ligand binding to the central metal of a metalloporphyrin. Porphyrin coordination assemblies, where the oligomerization interaction involves a peripheral ligand on the porphyrin coordinated to an external metal ion, are also prepared. Metalloporphyrins can also self-assemble in a cooperative open arrangement, generating polymeric structures with additional stability because of the intramolecular ring closure processes.
Self-assembly of porphyrin arrays / Baldini, Laura; Hunter, C. A.. - In: ADVANCES IN INORGANIC CHEMISTRY. - ISSN 0898-8838. - 53:(2002), pp. 213-259. [10.1016/S0898-8838(02)53006-3]
Self-assembly of porphyrin arrays
BALDINI, Laura;
2002-01-01
Abstract
This chapter discusses self-assembly of porphyrin arrays. Porphyrins represent ideal building blocks for the synthesis of oligomeric and polymeric arrays through the self-assembly technique. They are rigid, can easily be functionalized, and a number of different metals can be inserted in the center of the macrocycle. The central metal of the porphyrin is coordinated to four nitrogens and can accept either one or two additional apical donor atoms to give a square pyramidal or octahedral coordination sphere respectively. A number of self-assembled porphyrin arrays have been reported, held together by either hydrogen-bonding or metal–ligand coordination interactions. The chapter focuses on coordination oligomers where the key oligomerization interactions involve ligand binding to the central metal of a metalloporphyrin. Porphyrin coordination assemblies, where the oligomerization interaction involves a peripheral ligand on the porphyrin coordinated to an external metal ion, are also prepared. Metalloporphyrins can also self-assemble in a cooperative open arrangement, generating polymeric structures with additional stability because of the intramolecular ring closure processes.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.