New effective synthons for supramolecular self-assembly of meso-carboxyphenylporphyrins

Abstract

Tesselation of new supramolecular motifs of the tetra(4carboxyphenyl)porphyrin building blocks by metal ion templates has been demonstrated in crystals, characterizing the square-planar [Na + •(-COOH) 4 •X 2 ] and the tetrahedral [Zn 2+ •(-COOH) 2 •(-COO 2 ) 2 ] molecular recognition elements for effective multiporphyrin assembly.

Metalloporphyrin Molecular Sieves

“…[23] Such templates may provide higher enthalpic driving force for the self- Figure 5. In this context, we have formulated extended networks of the TCPP tecton through multiple coordination of metal ion templates to partly deprotonated carboxylic substituents.…”

“…In this context, we have formulated extended networks of the TCPP tecton through multiple coordination of metal ion templates to partly deprotonated carboxylic substituents. [23,24] The former yield either flat or diamondoid multiporphyrin networks depending on the coordination geometry around the metal ion templates: square-planar (around Na ) or tetrahedral (around Zn 2 ). Top: Supramolecular networks of the large Zn II TDTPP building blocks sustained by multiple hydrogen bonds.…”

“…[23] Such templates may provide higher enthalpic driving force for the self- Figure 5. [23] In the solid, the flat arrays are effectively held together in an overlapping manner by stacking p ± p interactions with about 0.6 nm wide channels, which are accessible by guests, propagating through the layers in the normal direction. The distance between opposite van der Waals walls of the interporphyrin void space is about 2.2 nm.…”

62 Porphyrin-Based Tectons in Molecular Tectonics

“…The external Zn(II) cation is coordinated to four porphyrin units ( Figure 22). 74 The Zn(II) located within the porphyrin core is penta-coordinated, with one molecule of solvent (ethylene glycol) occupying the axial position. The 3D networks are interpenetrated and the solvent molecules present in the channels can be exchanged with other guest molecules.…”

“…The formation of a wavy 2D open network resulting from the interconnection of consecutive neutral porphyrin derivative H 2 (PCOOH) 4 Po bearing four carboxylic acid moieties by Na + cations has been reported by Goldberg and coworkers. 74 Each Na + cation is surrounded by four adjacent porphyrins in an approximate square planar arrangement (with Na-O distances of ca. 2.34 Å) ( Figure 15).…”