The unique properties of porous metal-organic frameworks are responsible for the increasing research interest in the design and synthesis of this type of materials. A general strategy towards targeted design of metal-organic frameworks possessing desired properties is a choice of optimal linkers, which are usually represented by polytopic organic ligands. Porphyrins are promising building blocks for such frameworks due to their tunable physicochemical properties and wide possibilities of macrocycle modification. The achievements of the last decade in the development of synthetic approaches to porphyrin functionalization have promoted fast progress of tetrapyrrole chemistry as the basis of metal-organic frameworks. This review gives analysis of the current literature devoted to the synthesis of porphyrin-based metal-organic frameworks and the prospects for their application in modern materials science. The bibliography includes 262 references.

Evolutionary selection in nature has led to hierarchical structuring as a fundamental optimization strategy for biological structures, maximizing functional performance while minimizing resource usage. Precise hierarchical organization of natural materials over a wide range of length scales gives rise to unique synergistic properties that could not be achieved by single components. Despite the clear advantages offered by hierarchically structuring matter, mastering hierarchical control based on the current synthetic toolbox is still a challenge. In this review, some recent advancements in the fabrication of hierarchical metal organic framework (MOF) materials are highlighted and the advantages that arise due to different kinds of MOF hierarchy are critically analyzed. The special focus of the review lies in highlighting the applications where MOF hierarchical materials can be most impactful and describing characterization techniques currently at the disposal of scientists for the precise characterization of MOF hierarchical structures across all length scales. Finally, the intent is to inspire reticular chemists to master hierarchical control of MOF materials so as to fully utilize the advantages MOFs offer for various applications.