Photosensitive supramolecular systems have garnered attention due to their potential to catalyze highly specific tasks through structural changes triggered by a light stimulus. The tunability of their chemical structure and charge transfer properties provides opportunities for designing and developing smart materials for multidisciplinary applications. This review focuses on the approaches reported in the literature for tailoring properties of the photosensitive supramolecular systems, including MOFs, MOPs, and HOFs. We discuss relevant aspects regarding their chemical structure, action mechanisms, design principles, applications, and future perspectives.

Metal–organic cages (MOCs) are discrete supramolecular entities consisting of metal nodes and organic connectors or linkers; MOCs are noted for their high porosity and processability. Chemically, they can be post-synthetically modified (PSM) and new functional groups can be introduced, presenting attractive qualities, and it is expected that their new properties will differ from those of the original compound. This is why they are highly regarded in the fields of biology and chemistry. The present review deals with the current PSM strategies used for MOCs, including covalent, coordination, and noncovalent methods and their structural benefits. The main emphasis of this review is to show to what extent and under what circumstances a MOC can be designed to obtain a tailored geometric architecture. Although sometimes unclear when examining supramolecular systems, particularizing the design of and systematic approaches to the development and characterization of families of MOCs provides new insights into structure–function relationships, which will guide future developments.

Metal–organic cages (MOCs) are discrete supramolecular entities consisting of metal nodes and organic connectors or linkers, in addition to having high porosity and processability. Chemically, it is admirable that they are feasible to be post-synthetically modified (PSM) and introduce new functional groups, so it is to be expected that the properties will be different from those of the original compound. This is why they are highly regarded in the fields of biology and chemistry. The present work is dealing with the current PSM strategies used for MOCs, including covalent, coordination and noncovalent methods and its structural benefits. The main emphasis of the work is to show what extent and under what circumstances a MOC can be designed to obtain a tailoring geometrically architecture. Although sometimes remain unclear when looking at supramolecular systems by particularizing the design and their systematic approaches on the development and characterization of families of MOCs, thereby, our new insight about structure–function of MOCs relationships will escort to future developments.

Supramolecular structures with specific applications are a pillar in several areas of science. Thus, from a contemporary point of view, there are several reasons to feel inclined to cover a systematic, or historic critique of the supramolecular concept itself. First, the idea of a supramolecular material seems more secure now than it was decades ago. Second, updating the interacting of MOFs and supramolecular chemical and conversely, supramolecularity to assemble MOFs and to make ef-ficient complex systems in multiple cutting-edge applications. Third, we should here simply confine to a consideration of how workers in this field have tried to correlate the notion of the idea of supramolecular systems linking self-assembly considerations. Thereby, this is clearly an ad-vantage that optimized geometries obtained on the conductive bases described that undoubtedly, some of these systems have substantial applications and create a significant practical interest. The outline of this review encompasses a general introduction to MOFs and supramolecularity, the key unit of the study presented here, followed by a survey of recent advances in supramolecular chemistry in confined space, relationships of MOFs with the supramolecular chemistry, electro-chemical synthesis of MOFs, and switchable MOFs. Finally, some discussion on possible future perspectives of this field is given.