Meso-Fused Carbatriphyrins(2.1.1) and Its Organo Phosphorus(V) Complex.

The first examples of phlorin analogues of meso-fused carbatriphyrins(2.1.1) and organo P(V) complex of one of the meso-fused carbatriphyrins were obtained by adopting a premodification strategy starting with fluorene as a fused polyaromatic precursor over a sequence of steps. The meso-fused carbatriphyrins(2.1.1) were obtained as their nonaromatic phlorin analogues owing to the unstable nature of the fully conjugated meso-fused carbatriphyrins(2.1.1). The organo P(V) complex of one of the meso-fused carbatriphyrins was prepared by treating the phlorin analogue of carbatriphyrin(2.1.1) with PCl3 in toluene/triethylamine at reflux for 1 h. The P(V) complex of the meso-fused carbatriphyrin(2.1.1) was found to be moderately aromatic and the resulting global conjugation pathways in the P(V) complex significantly alters the aromaticity of the fluorene unit. The nonaromatic nature of the phlorin analogues of the meso-fused carbatriphyrin(2.1.1) and the moderately aromatic nature of its P(V) complex were supported by X-ray crystallography, absorption spectroscopy, NMR studies together with nucleus-independent chemical shifts, anisotropy-induced current density, and harmonic oscillation stabilization energy calculations.