Annulene porphyrin-related

The successful preparation of porphyrinic molecular conductors has recently led to initial studies of analogous metallomacrocycles with the M(N4), metal-ligand core, the dihydrodibenzotetraaza[14]annulenes and related complexes172-175. ... 

H NMR spectroscopic analysis (e.g., 8cH-inner = —16.0 ppm 5cH-outer = 13.8 and 14.7 ppm, in CF3CO2D). Macrocycle 7.85 also exhibits UV-vis absorption bands characteristic of highly conjugated porphyrin-related annulenes. For instance, in 5% TFA in CH2CI2, system 7.85 exhibits one fairly intense Soret-like band at 667 nm... 

A theoretical study of the acidity (proton loss) of the porphyrin 266 and some related systems was carried out by means of the B3LYP/6-31+G(d,p) computational level. These include, on one hand, porphyrin fragments 267 and pyrrole 11 (X = H) and the monoanion and dianion of 266 and, on the other hand, chalcogen-related porphyrins 268,269, and 270 and their anions, as well as cyclic nitrogen derivatives 271, 272, 273, and 274, simplified models of porphyrin, dibenzo[14]annulene, phthalocyanine, and porphycene. 

A metal ion M as part of a polymer chain is surrounded by a multivalent ligand. As a result, stacked arrangements 107 are realized with a face-to-face orientation of the ligands. Porphyrins, phthalocyanines, naphthalocyanines, etioporphyrin, tetraaza[14]annulene, hemiporphyrazines, and related macrocycles as ligands have been most intensively investigated. Because several reviews summarize preparations and properties (conductivity, photoconductivity, NLO, electroluminescent detectors) of these materials, only a short overview on these polymers is given [1,3,34,40,375-377]. Several years ago, unsubstituted macrocycles were employed as ligands. These polymers are much less soluble. Recently, the use of substituted macrocycles has led to soluble polymers which are analytically easier to characterize. 

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