Unlocking the computational design of metal–organic cages

Abstract

Metal-organic cages are macrocyclic structures that can possess an intrinsic void that can hold molecules for encapsulation, adsorption, sensing, and catalysis applications. As metal-organic cages may be comprised from nearly...

Assembling metal–organic cages as porous materials

“…59,60 Nonetheless, there are some approaches to computer-aided cage design and hostguest binding predictions. 61,62 The development of structureproperty relationships in MOCs is also hindered by a lack of structural information for solvent-exchanged polycrystalline phases and activated phases, which is still mostly limited to use of powder X-ray diffraction to illustrate changes in packing. 63 Amorphous, cross-linked MOCs present a greater challenge for their structural characterisation.…”

Advances in the Structural Strategies of the Self-Assembly of Photoresponsive Supramolecular Systems

“…However, there has been a trend to develop more sophisticated and functional MOCs by self-sorting diverse ligands into heteroleptic cages, unsymmetrical ligands into asymmetrical MOCs, or ligands with secondary functionalities into functional materials. The extremely large availability of MOC precursors allows researchers to tailor them for specific properties [ 56 , 57 ]. Moreover, their discrete, rather than extended, structures with well-defined shapes, specific cavities, nano-scale sizes, and symmetrical geometries allow them to be used as self-sufficient materials in a wide range of applications but also to tune soft materials used in medicine, robotics, and battery research [ 58 ].…”

Catalysis by [Ga4L6]12− Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key

“…It provides detailed understanding of the processes that is not easily accessible by experimental techniques. In the case of supramolecular catalysis, computational methods have only been applied recently mainly because of the large dimensions of the systems [21–23,32–44] …”

“…In the case of supramolecular catalysis, computational methods have only been applied recently mainly because of the large dimensions of the systems. [21][22][23][32][33][34][35][36][37][38][39][40][41][42][43][44] In the current contribution, we present a computational study with the aim of identifying the factors causing the rate enhancement of the Nazarov reaction inside the metallocage as compared to solution. We use a combination of quantum mechanical (QM) calculations and molecular dynamics (MD) simulations, and the overall description of the reaction mechanism is obtained by connecting experimental and computational results to describe the reaction steps for the process.…”