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The use of axial coordination to metalloporphyrins is discussed on the basis of constructing multinuclear complexes. Starting with single metalloporphyrin-ligand complexes where the ligand is designed to bring a functional moiety close to the porphyrin, the discussion further expands to the design, synthesis, and detailed analysis of multiporphyrin assemblies. The porphyrin-as-ligand concept combined...
The supramolecular organization of porphyrins using self-complementary coordination is reviewed. Complementarity affords large stability constants for coordination organization, and as a result various structural variations of porphyrin supramolecules were obtained. Dimeric porphyrins are of special interest as they mimic the special pair of the photosynthetic reaction centers. A very stable slipped...
The metal-driven construction of multi-porphyrin assemblies, which exploits the formation of coordination bonds between exocyclic donor site(s) on the porphyrins and metal centers, has recently allowed the design and preparation of sophisticated supramolecular architectures whose complexity and function begin to approach the properties of naturally occurring systems. Within this framework, meso-pyridyl/phenyl...
Re(CO)5Cl readily reacts with pyridine-derivatized porphyrins to give molecular squares or planar dimers featuring fac-Re(CO)3(Cl) corners. Chelating ligands, in sequential combination with pyridine-derivatized porphyrins, can be used to obtain related cofacial porphyrin assemblies. Films and membranes displaying molecular-scale porosity can be generated from squares by: (1) van...
An overview of the thermodynamic principles governing self-assembly in solution, with particular reference to multiporphyrin architectures, is presented. The topic is discussed in order of increasing complexity, from simple acyclic assemblies to multicyclic assemblies, by emphasizing the role played by two fundamental physicochemical quantities, namely, the stability constant of the metalloporphyrin-ligand...
The approach based on the copper(I)-templated synthesis of porphyrin catenanes and rotaxanes developed by the authors' group is here reviewed. Zn(II) porphyrins and gold(III) porphyrins were chosen as electron donors and electron acceptors, respectively, to constitute the electro- and photoactive parts of the present systems. The processes—energy and electron transfer reactions—occurring in the interlocked...
Although relatively weak in isolation, composite H-bonds can be used as an advantage for the assembly of relatively robust and well-defined arrays of molecular components. Porphyrins, with their inherent symmetry, synthetic accessibility and functionality offer ideal base units for the assembly of multicomponent systems by the reversible yet strong intermolecular forces of H-bonding. The geometric...
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