Multiporphyrin arrays, self-assembled

Inorganic templating and self-assembly provide coordination compounds whose geometries make possible the synthesis of complex structures, namely of cyclic multiporphyrin arrays [9.13a, 9.179], of inorganic rotaxanes [9.97a, 9.180], of multi-catenates and catenands (see 181) [8.281, 8.282] and even of molecular knots (see 182) [8.282, 9.77, 9.181] (in 181 and 182 a) with, b) without Cu(l) template). 

Stang et al. [94JA4981, 9403776, 95JA1667, 95JA6273] described the self assembly of a series of unique cationic, tetranuclear, Pd(II)- and Pt(II)-based macrocyclic squares (e.g., 25), utilizing different bidentates as the sides of these structures. The similar self-assembly complexation of dipyridyl porphyrins by cis- and tran.v-substituted Pd(II) or Pt(II) ions possessing square planar coordination afforded multiporphyrin arrays with a square... 

Self-assembly principles of the formation of multiporphyrin arrays are extended to anchor the porphyrin triads on semiconductor CdSe/ZnS quantum dot (QD) surface. Comparing with individual counterparts (QD, pyridylsubstituted porphyrin H2P(p-Pyr)4, and Zn-octaethylporphyrin chemical dimer (ZnOEP Ph), the formation of heterocomposites QD-porphyrin triad results in the specific quenching of QD photoluminescence, accompanied by the dimer fluorescence strong quenching (Tsd 1-7 ps due to energy and/or electron transfer) and the noticeable decease of the extra-ligand H2P(p-Pyr)4 fluorescence efficiency by 1.5-2 times via hole transfer H2P—>dimer. 

Drain, C.M. and J.M. Lehn (1994). Self-assembly of square multiporphyrin arrays by metal-ion coordination./. Chem. Soc. Chem. Commun. 2313-2315. 

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