Multiporphyrin architectures

An overview of the thermodynamic principles governing self-assembly in solution, with particular reference to multiporphyrin architectures, is presented by Gianfranco Ercolani in the fifth chapter. The topic is discussed in order of increasing complexity, from simple acyclic assembhes to multi-cyclic assemblies. The principles are illustrated by selected examples of metal-mediated assemblies of porphyrins, many of which have been described in the previous chapters. 

Krishna Kumar, R. Balasubramanian. S. Goldberg. I. Supramolecular multiporphyrin architecture. Coordination polymers and open networlis in crystals of tetrakis(4-cyanophenyl)- and tetrakis(4-nitrophenyl)-metallopor-phyrin. Inorg. Chem. 1998, 37. 541-552. 

Diskin-Posner, Y. Patra. C.K. Goldberg. I. Crystal engineering of 2-D and 3-D multiporphyrin architectures— The versatile topologies of tetracarboxyphenylporphyrin-based materials. Eur. J. Inorg. Chem. 2001. 2515-2523. 

Topics which have formed the subjects of reviews this year include excited state chemistry within zeolites, photoredox reactions in organic synthesis, selectivity control in one-electron reduction, the photochemistry of fullerenes, photochemical P-450 oxygenation of cyclohexene with water sensitized by dihydroxy-coordinated (tetraphenylporphyrinato)antimony(V) hexafluorophosphate, bio-mimetic radical polycyclisations of isoprenoid polyalkenes initiated by photo-induced electron transfer, photoinduced electron transfer involving C o/CjoJ comparisons between the photoinduced electron transfer reactions of 50 and aromatic carbonyl compounds, recent advances in the chemistry of pyrrolidino-fullerenes, ° photoinduced electron transfer in donor-linked fullerenes," supra-molecular model systems,and within dendrimer architecture,photoinduced electron transfer reactions of homoquinones, amines, and azo compounds, photoinduced reactions of five-membered monoheterocyclic compounds of the indigo group, photochemical and polymerisation reactions in solid Qo, photo- and redox-active [2]rotaxanes and [2]catenanes, ° reactions of sulfides and sulfenic acid derivatives with 02( Ag), photoprocesses of sulfoxides and related compounds, semiconductor photocatalysts,chemical fixation and photoreduction of carbon dioxide by metal phthalocyanines, and multiporphyrins as photosynthetic models. 

Two of the classical bis-nitrogen ligands to assemble porphyrins (predominantly zinc metallated) are the bidentate l,4-diazabicyclo[2.2.2]octane (DABCO) and 4,4 -bipyridine (bipy). Other di-topic nitrogen-ligands studied include hydrazine, 4,4 -bipyrimidine, diaza-pyrene, 5,5 -dicyano-2,2 -bipyri-dine, perylene-bisimide, extended bipyridine units and non-covalently linked di-pyridyl ligands via bipy-metal interactions. The formation of various bis-porphyrin and multiporphyrin assemblies using these versatile ligands were studied in detail by Sanders, Anderson, Hunter, Branda and many others. The structures of the supramolecular multi-porphyrin architectures are schematically represented in Fig. 9. 

Durot S, Taesch J, Heitz V. Multiporphyrinic cages architectures and functions. Chem Rev 2014 114 8542-78. 

Jiao J, Anariba E, Tiznado H, Schmidt I, Lindsey JS, Zaera F, Bocian DE (2006) Stepwise formation and characterization of covalently linked multiporphyrin-imide architectures on Si (100). J Am Chem Soc 128(21) 6965-6974... 

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