A thermoresponsive, 3D hinged metal-organic framework (HMOF-1) assembled from meso-tetra(4-pyridyl)porphine and CdI(2) exhibits a 3D "lattice fence" topology with extraordinary thermal expansion and shrinkage. A simple structural model is established to elucidate such a drastic thermal response. The hinged structure model presented here can also be applied to other "lattice fence" topologies with little or no modification, depending on the symmetry of the molecular building blocks.

In this review, we classify 1D, 2D, and 3D structural motifs found in porphyrinic coordination polymers assembled from 5,10,15,20-tetrapyridylporphyrin (TPyP) and its derivatives. The classifications are based on dimensionality, metal-to-porphyrin linkage, porphyrin type, and metal-to-porphyrin ratio. 1D porphyrin polymers often share the same connectivity (or structural motifs) with analogous 2D and 3D polymers. We identify interrelationships among 1D, 2D, and 3D coordination polymers and examine the connectivity of such interrelated structures. We also discuss the broad similarities and differences of the synthetic methods of all structures presented here.

A novel porphyrin-based metal−organic framework (MPF-3) was synthesized by the solvothermal reaction of Zn(NO3)2·6H2O and meso-tetra(3-pyridyl)porphine in N,N-dimethylformamide (DMF). Its structure was characterized by single crystal X-ray diffraction and found to be a two-dimensional (2D) interdigitated framework in which DMF solvent molecules reside between the interdigitated layers. The observed 2D topology can be related to the Cairo pentagonal tessellation. X-ray powder diffraction reveals that MPF-3 undergoes a phase transformation when the solvent molecules are removed by heating. Surprisingly, the original topologies are restored when the desolvated phase is immersed in DMF, thereby demonstrating the flexibility of the framework.

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