Oxasmaragdyrin-ferrocene and oxacorrole-ferrocene conjugates: synthesis, structure, and nonlinear optical properties.

Ferrocenyl macrocyclic conjugates involving 22 pi oxasmaragdyrins and 18 pi oxacorroles have been synthesized and characterized. The direct covalent linkage of the ferrocenyl moiety to the meso position of the macrocycle is achieved by simple oxidative coupling of appropriate precursors with trifluoroacetic acid as catalyst. The electronic coupling between the ferrocenyl moiety and the macrocyclic pi system is apparent from: a) the red shifts (293-718 cm(-1)) of the Soret and Q-bands in the electronic absorption spectra of ferrocenyl conjugates; b) the shift of oxidation potentials (50-130 mV) of both the ferrocene and the corrole rings to the positive potentials; and c) considerable shortening of the C-C bond which connects the ferrocene and the meso-carbon atom of the macrocycle.

Core-modified expanded porphyrins: new generation organic materials.

Even though the first expanded porphyrin was reported in the mid-1960s, the advances in its chemistry are more recent. New and powerful synthetic methods have facilitated the availability in affordable quantities of expanded porphyrins in general and core modified systems in particular. This has stimulated interest in studying various properties pertaining to their potential applications in biomedicine and materials chemistry.

meso-substituted aromatic 34pi core-modified octaphyrins: syntheses, characterization and anion binding properties.

Modified octaphyrins with 34pi electrons have been synthesized and characterized following a simple synthetic methodology. An acid-catalyzed alpha,alpha coupling of tetrapyrranes containing furan, thiophene and selenophene rings resulted in the formation of the respective octaphyrins in relatively good yield. Solution studies by (1)H NMR and 2D NMR methods and single crystal Xray structural characterization reveal an almost flat structure with two heterocyclic rings inverted.

Modified corroles with one meso-free carbon: synthesis and characterization.

[reaction: see text] Synthesis of mono meso-free modified corroles by a [3+1] methodology is reported.

First structural characterization of core modified 10,15-meso aryl azuliporphyrins: observation of C-H...pi interaction between pyrrole beta-CH and mesityl ring.

First successful syntheses and structural characterization of new core modified meso aryl azuliporphyrins by a simple [3 + 1] methodology are reported.

Core modified oxybenziporphyrins: new aromatic ligands for metal-carbon bond activation.

Successful syntheses of two new aromatic core modified oxybenziporphyrins by a simple '3 + 1' methodology and the first aromatic core modified oxybenziporphyrin palladium complex are reported.