Separation and Selective Formation of Fullerene Adducts within an M^II₈L₆ Cage

Abstract

The self-assembly of 4-fold-symmetric porphyrins with Fe or Zn gave a new cubic ML cage framework with electron-deficient walls. This cage bound C-indene or C-anthracene bisadducts selectively, whereas unfunctionalized fullerenes and monoadducts were not encapsulated. The FeL cage also enabled the reaction of C and anthracene to yield the bisadducts selectively under conditions where no reaction was observed in the absence of the cage. These findings have relevance in the context of polymer solar cells, where C bisadducts have found use as electron acceptors, because these adducts currently require laborious and time-consuming syntheses and purification.

Selective C70 encapsulation by a robust octameric nanospheroid held together by 48 cooperative hydrogen bonds

“…Most of the alternative methods for fullerene separation and purification are only selective towards the major component C 60 49; examples in the literature in which C 70 are preferred are scarce. Although a few examples of C 70 and C 60 fullerenes and receptors have been reported, they were mainly based on the dimeric structures50, or metal-ligand coordinative bonds4951525354. The presented system consist on purely organic and multimembered spheroidal architecture and for reasons of synthetic economy it provides a major advantage since only one molecule is needed to generate selective receptor for fullerenes.…”

Positive Allosteric Control of Guests Encapsulation by Metal Binding to Covalent Porphyrin Cages

“…Porphyrins are attractive as active components for artificial allosteric systems due to their involvements in many biological processes through their binding, redox or photophysical properties. Especially, structures incorporating metalloporphyrins with a defined binding pocket have shown molecular recognition properties and catalytic activity …”

“…Especially,s tructures incorporatingm etalloporphyrins with ad efined binding pocket have shown molecular recognition properties andc atalytic activity. [11,[59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74][75] Our previous work has focused on the synthesis of coordination [76] andc ovalent architectures incorporating metalloporphyrins. [77][78][79] In particular,f lexible covalent cages incorporating orthogonal binding sites, metalloporphyrins and 1,2,3-triazoles, were obtained using aD ABCO-templated copper(I)-catalyzed alkyne-azider eaction (DABCO = 1,4-diazabicyclo[2.2.2]octane).…”

Supramolecular Maleate Adducts of Copper(II) 12‐Metallacrown‐4: Magnetism, EPR, and Alcohol Sorption Properties

“…Polynuclear complexes and supramolecular assemblies with porous lattices based on polynuclear blocks are attracting attention as the potential basis for multifunctional materials due to their ability to absorb different substrates, as well as other physical properties Inasmuch as the properties of the starting compound – the “building block” – usually pre‐determine the properties of the resultant coordination polymer or supramolecular assembly based on it, the choice of building block is important. The combination of physical and chemical properties of the chosen block with the ability of a porous lattice in the resulting compound to interact with certain substrates enables use of these assemblies as active constituents of sensors,, as magnetic, or luminescent, materials with tunable properties, as sorbents,, or in separation processes …”