N-Confused Double-Decker Porphyrins

Abstract

An inner-coordinated Pd complex and inner- and outer-N coordinated, double-decker Pd complexes of N-confused tetratolylporphyrin have been synthesized, and their structures were elucidated by X-ray single-crystal analyses.

Facile Formation of N‐Confused Porphyrin Dimers by Platinum(II) Coordination to the Outer‐Nitrogen Atoms

“…[5] The unique structure of 2 was derived as the result of the distortion from planarity of both the porphyrin ring and the coordinated Pd II center. In this regard, we have been interested in Pt II -ion complexation because rigid square-planar Pt II complexes are known.…”

“…Interestingly, the Pt dimer complexes (3, 4) were singly linked dimers with the ratio of Pt to NCP being 1:2. Herein, we report the syntheses and structural characterization of novel Pt II -NCP dimer complexes and an inner coordinated monomer complex (5). To the best of our knowledge, the complexes 3 and 4 are the first NCP dimers linked by a metal at the peripheral core nitrogens.…”

A Perspective of One‐Pot Pyrrole–Aldehyde Condensations as Versatile Self‐Assembly Processes

“…For example, the centrally C-deprotonated form of the ligand can act as both a dianionic and a trianionic ligand for divalent and trivalent transition metal ions, respectively. Thus, Ni II , Ni III , [59] Pd II , [52] Ag III , [60] and Mn III [61] complexes with approximately planar CTPP/CTTP ligands have been reported (Scheme 3). However, the central carbon atom tends to remain protonated in a number of transitionmetal-CTPP derivatives, in particular in Cu II , [62,63] Zn II , [64] high-spin Mn II , [65] and high-spin Fe II complexes [66] (Scheme 5).…”

“…[65,66] Finally, the outer nitrogen atom can also participate in metal-ion coordination to give dimeric and other complex structures (Scheme 5). [52,[64][65][66][67][68] It is interesting to note that the availability of N-confused porphyrins through one-pot pyrrole-aldehyde condensations is largely limited to (CTPP)H 3 and (CTTP)H 3 at present. There have been no reports of practical, one-pot access to Nconfused porphyrins with meso substituents, such as alkyl groups, perfluoroalkyl groups, or aryl groups with electronegative substituents.…”

Experimental and Theoretical Studies on Oligomer Formation of N‐Confused Porphyrin–Zinc(II) Complexes

“…[12][13][14] In the former complexes, the confused pyrrole moieties inclined typically in 40-458 relative to the porphyrin planes so as to form homodimers. Based on previous results on NCP derivatives bearing the inverted conformation [15] and the formation of Nfused porphyrin at ambient temperature, [16,17] the angles between the porphyrin planes and the confused pyrrole plane should vary.…”