The synthesis and spectroscopic properties of a series of boron-free meso-aryl-substituted [14]triphyrin(2.1.1) compounds containing either peripheral bicyclo[2.2.2]octadiene (BCOD) (2a−c) or benzene rings (3a−c) (aryl = phenyl a, 4-fluorophenyl b, and 4-methylbenzoatephenyl c) are reported. These compounds represent the first examples of free-base contracted porphyrinoids with 14 π-electron aromatic systems containing only the standard pyrrole and isoindoline moieties of the porphyrins and tetrabenzoporphyrins.

The metal-free and meso-free [14]triphyrin(2.1.1) compound was successfully prepared based on the intramolecular McMurry coupling reaction of diformyl-tripyrrane in 16% yield, and was converted to the bowl-shaped Mn(I)(TriP)(CO)(3) and Re(I)(TriP)(CO)(3).

A new class of boron-dipyrromethene (BDP or BODIPY) dyes was obtained by phenanthrene fusion to the beta-pyrrole positions, absorbing in the wavelength range of important laser sources. Despite a 'propeller-like' distorted structure in the crystalline state, the chromophore absorbs (log epsilon > or = 5) and fluoresces (Phif > or = 0.8) strongly and can be easily turned into a fluorescence light-up probe. Incorporation into latex beads produces bright and photostable single-dye and Förster Resonance Energy Transfer (FRET) particles for microscopy applications.