Self-Assembled Coordination Cages and Organic Capsules as Catalytic Supramolecular Reaction Vessels

Network topology and cavity confinement-controlled diastereoselectivity in cyclopropanation reactions catalyzed by porphyrin-based MOFs

“…The abovementioned stabilization is also known from cagecatalyzed reactions leading to unusual reactivity/selectivity compared to their bulk counterparts. 10,49,50 Further, we investigated the conversion of 4-hydroxystyrene and we found a similarly high dr of 21:1 (trans:cis), which supports the idea of the directing group effect of the substrate. However, the yield of the corresponding cyclopropane was low due to side reactions with propylene glycol, which is present in the solution of 4-hydroxystyrene (10 wt%), acting as a stabilizer.…”

Self-Assembly of Catalytically Active Supramolecular Coordination Compounds within Metal–Organic Frameworks

“…This is exemplified by the few reactions reported with the archetypal roughly spherical polyhedra of general formula Pd n L 2 n , in catalytic amounts, − as well as by the need to build up ensembles with already known catalytically active metalloligands as linkers. − Thus, a new avenue for research may be opened by finding ways to exploit the metal catalysis of the pivotal metal atoms from which the SCCs are built. The implementation of such a challenging task is relevant in two ways: ( i ) unprecedented functional SCCs could be developed, otherwise not accessible, which may have a significant impact on other related research areas, and ( ii ) the catalytic potential of pivotal metal atoms could be fully unleashed, which would widen the scope of supramolecular catalysis. − …”

Calix[6]arene-Based [3]Rotaxanes as Prototypes for the Template Synthesis of Molecular Capsules

“…These assemblies are of particular interest in the development of containers that can provide stability to highly reactive guests [ 8 , 9 ], such as phosphonium cations [ 10 ], cyclobutadiene [ 11 ], or even reactive elemental white phosphorus [ 12 ]. Capsular assemblies create a cavity in which the guest molecules frequently exhibit modifications as consequences of the confinement and, therefore, might be exploited as nanoscale “flasks” or reactors able to manipulate the physical and chemical properties of the trapped species [ 13 , 14 ]. A peculiar class of molecular capsules is one in which the hollow cavity is composed of two hemispherical or curved molecules.…”