Coordination polymers of tetra(4-carboxyphenyl)porphyrins sustained by tetrahedral zinc ion linkers

Michaela Shmilovits, Mikki Vinodu, Israel Goldberg*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Reactions between the free base tetra(4-carboxyphenyl)porphyrin and the corresponding platinum or palladium metalloporphyrin derivatives with zinc acetate dihydrate under solvothermal conditions in a basic environment (in the presence of pyridine and ammonium hydroxide) yielded extended supramolecular networks. These polymeric arrays consist of fully deprotonated porphyrin carboxylate units interconnected to each other by Zn(H2O) 22+ auxiliaries. The zinc ion linkers adapt a tetrahedral coordination environment, imparting to the polymeric network an open three-dimensional architecture, wherein each zinc binds to two adjacent porphyrin units and two water ligands, while every porphyrin entity is linked to four different metal centers. In a reaction involving the free base macrocycle, the zinc ions were inserted into the porphyrin core as well, forming a five-coordinate entity with pyridine as an axial ligand. The solid state syntheses yielded either one-dimensional ladder type coordination polymers that pair in an interlocking manner or three-dimensional diamondoid arrangements with interpenetrating polymeric networks. Both types of frameworks are further interlinked to each other by weak hydrogen bonds from the zinc-bound water ligands of one array to the carboxylate functions of another. The previously reported porphyrin-based polymer tessellated by Zn2+ linkers that coordinate at a given binding site to four (rather than two) porphyrin units is also discussed.

Original languageEnglish
Pages (from-to)633-638
Number of pages6
JournalCrystal Growth and Design
Issue number3
StatePublished - May 2004


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