A calcium-bridged porphyrin coordination network

Abstract

The hydrothermal assembly of a very stable porphyrin network with nanoscale cavities is described. A tightly packed and interpenetrated, linear polymeric framework was observed in the solid-state X-ray structure of freebase 5,10,15,20-tetrakis-(4-carboxyphenyl)porphyrin coordinated to calcium(II) ions. Strong hydrogen-bonding interactions between the coordination polymers form a two-dimensional network. Perpendicular bands interpenetrate generating an unusual three-dimensional box that clathrates a pyridine molecule.

Microporous Porphyrin and Metalloporphyrin Materials

“…17). Hydrogen bonding between coordinated water molecules in the calcium layers was observed to stabilize the three-dimensional structure (23). The independent linear polymers are structurally similar to those observed for the T(p-OH)PP hydrogen bonded networks by Strouse and coworkers (Fig.…”

Porphyrin–Alkaline Earth MOFs with the Highest Adsorption Capacity for Methylene Blue

“…Compared to the intense study over the symmetrical tetrakis(4‐pyridyl)porphyrin and tetrakis(4‐carboxyphenyl)porphyrin, which have been extensively used to construct diverse metal–organic frameworks, complexes based on 5,15‐di(4‐carboxyphenyl)porphyrin (H 2 DCPP) ligand have been rarely reported, only limited to DBP‐UiO . As can be easily expected, in contrast to the intensive studies over the transition‐metal‐based porphyrin MOFs, the main group alkaline earth metal‐based porphyrin MOFs still remain relatively undeveloped with the calcium‐based MOF, C 48 H 26 N 4 O 8 Ca 2 ⋅ 4 H 2 O ⋅ C 5 H 5 N, as the sole example reported thus far . As a consequence, design and synthesis of porphyrin–alkaline earth metal–organic frameworks appear to be not only a great challenge but also highly desired in this area.…”

“…[12] As can be easily expected, in contrast to the intensives tudies over the transition-metal-based porphyrin MOFs, [13] the main group alkaline earth metal-based porphyrin MOFs still remainr elatively undeveloped with the calcium-basedM OF,C 48 H 26 N 4 O 8 Ca 2 ·4H 2 O·C 5 H 5 N, as the sole exampler eported thusf ar. [14] As ac onsequence, designa nd synthesiso fp orphyrin-alkaline earth metal-organic frameworks appear to be not only agreat challenge but also highly desired in this area. On the other hand, adsorption of toxic and carcinogenic organic dyes by porous MOFs has received considerable attention in recent years as as imple and effective method for dye removal among various chemical, physical, and biological processes.…”

62 Porphyrin-Based Tectons in Molecular Tectonics

“…80 The four carboxylate groups act as bidentate ligands and bind calcium ions (with Ca-O distances of ca. 2.5 Å).…”