Modified 26 and 28 pi hexaphyrins with five meso-links: optical, redox, and structural properties.

The syntheses of new aromatic 26pi and non-aromatic 28pi hexaphyrins through a [4+2] acid catalyzed condensation of easily available and air-stable precursors are reported. Both 26pi and 28pi hexaphyrins are reversibly transformed into one another by two-electron reduction with NaBH(4) or two-electron oxidation with dichlorodicyanobenzoquinone (DDQ) respectively. Detailed optical and NMR spectral studies suggests that the [26]hexaphyrin is aromatic and possesses a diatropic ring current, while [28]hexaphyrin exhibits non-aromatic characteristics.

One-pot synthesis of oxidized and reduced heptaphyrins with unusual TFA binding.

Synthesis and reversible redox interconversion between core-modified [32]heptaphyrin (1.1.1.

meso-meso-Linked corrole dimers with modified cores: synthesis, characterization, and properties.

The synthesis and characterization of the first examples of core-modified corrole dimers linked through the meso positions are described. The dimers are obtained by a simple Ag(I)- or Fe(III)-catalyzed coupling reaction in near-quantitative yields. The corroles obtained are metalated with metal ions, such as Cu(II) and Ni(II).

Aromatic core modified decaphyrins with the largest two-photon absorption cross-sections: syntheses and characterization.

[structure: see text] Core-modified aromatic decaphyrins with 42pi conjugated electrons exhibit the highest two-photon absorption cross-section value (sigma(2) = 108,000 GM) known for any organic molecule, suggesting possible device applications in the field of nonlinear optics.

Aromatic core-modified twisted heptaphyrins[1.1.1.1.1.1.0]: syntheses and structural characterization.

[reaction: see text] First examples of aromatic core-modified twisted heptapyrrolic systems with six meso links have been obtained via a general [3 + 4] acid-catalyzed condensation method. Despite the twisted conformation, these heptaphyrins exhibit aromaticity in solution, unlike most of the all-aza analogues.

Core-modified expanded porphyrins with large third-order nonlinear optical response.

The third-order nonlinear optical response through measurement of two-photon absorption cross-sections (TPACS) for aromatic core-modified expanded porphyrin analogues by a femtosecond open aperture Z-scan method is reported. The values reported here are among the largest known so far in the literature for any organic molecules.

Modified expanded corrole-ferrocene conjugates: syntheses, structure and properties.

Syntheses, characterization and properties of expanded corrole-ferrocene conjugates are reported. Ferrocenyl group are covalently linked to the corrole macrocycle through three different spacers groups. The synthetic strategy involved prior insertion of ferrocene with spacers to the dipyrromethane unit followed by a "3+2" acid-catalyzed oxidative coupling methodology.

Figure-eight aromatic core-modified octaphyrins with six meso links: syntheses and structural characterization.

The synthesis and structural characterization of the first examples of aromatic core-modified figure-eight octaphyrins with six meso links and their formation with and without acid catalysts are highlighted.

Syntheses of core-modified corroles by three different [3 + 1] methodologies.

Three new methods for syntheses of modified oxa corroles bearing one meso free carbon in reasonably good yields are reported. The formation of the meso carbon bridge and the direct pyrrole-pyrrole linkage occur in a single step by a simple condensation and coupling with TFA as a catalyst with appropriate precursors. The reactions are optimized with different conditions by varying the meso substituents, acid catalyst concentration, and the nature of the solvent to afford corroles in good yields.

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.