An unprecedented and straightforward supramolecular mask strategy to prepare exclusively equatorial bis-, tris-, and tetrakis-cyclopropanated-C 60 Bingel-Hirsch derivatives is reported. By taking advantage of the high affinity for fullerene of tetragonal prismatic supramolecular cages, a highly stable C 60 31a$(BArF) 8 hostguest complex is submitted to Bingel-Hirsch cyclopropanation reaction conditions. Regioselectivity is strictly dictated by the four cross-shaped apertures of the nanocapsule in a controlled fashion. Moreover, stepwise-cyclopropanated adducts up to tetrakis additions are obtained in excellent yields and purities.
Supramolecular nanocapsule 1⋅(BArF) is able to sequentially and selectively entrap recently discovered U @C and unprecedented Sc CU@C , simply by soaking crystals of 1⋅(BArF) in a toluene solution of arc-produced soot. These species, selectively and stepwise absorbed by 1⋅(BArF) , are easily released, obtaining highly pure fractions of U @C and Sc CU@C in one step. Sc CU@C represents the first example of a mixed metal actinide-based endohedral metallofullerene (EMF). Remarkably, the host-guest studies revealed that 1⋅(BArF) is able to discriminate EMFs with the same carbon cage but with different encapsulated cluster and computational studies provide support for these observations.
The dynamic adaptability of tetragonal prismatic nanocapsule 1 8+ in the selective separation of fullerenes and endohedral metallofullerenes (EMFs) remains unexplored. Therefore, the essential molecular details of the fullerene recognition and binding process into the coordination capsule and the origins of fullerene selectivity remain elusive. In this work, the key steps of fullerene recognition and binding processes have been deciphered by designing a protocol which combines 1 H− 1 H exchange spectroscopy (2D-EXSY) NMR experiments, long time-scale Molecular Dynamics (MD) and accelerated Molecular Dynamics (aMD) simulations, which are combined to completely reconstruct the spontaneous binding and unbinding pathways from nanosecond to second timerange. On one hand, binding (k′ on ) and unbinding (k off ) rate constants were extracted from 1 H− 1 H exchange spectroscopy (EXSY) NMR experiments for both C 60 and C 70 . On the other hand, MD and aMD allowed monitoring the molecular basis of the encapsulation and guest competition processes at a very early stage under nonequilibrium conditions. The receptor capsule displays dynamical adaptability features similar to those observed in the process of biomolecular recognition in proteins. In addition, the encapsulation of bis-aza[60]fullerene (C 59 N) 2 within a supramolecular coordination capsule has been studied for the first time, showcasing the pros and cons of the dumbbell-shaped guest in the dynamics of the encapsulation process and in the stability of the final bound adduct. The powerful combination of NMR, MD, and aMD methodologies allows to obtain a precise picture of the subtle events directing the encapsulation and is thus a predictive tool for understanding host−guest encapsulation and interactions in numerous supramolecular systems.
We demonstrate the benefits of using cofacial Zn-porphyrins as structural synthons in coordination-driven self-assembled prisms to produce cage-like singlet oxygen ( O ) photosensitizers with tunable properties. In particular, we describe the photosensitizing and emission properties of palladium- and copper-based supramolecular capsules, and demonstrate that the nature of the bridging metal nodes in these discrete self-assembled prisms strongly influences O generation at the Zn-porphyrin centers. The Pd -based prism is a particularly robust photosensitizer, whereas the Cu self-assembled prism is a dormant photosensitizer that could be switched to a ON state upon disassembly of the suprastructure. Furthermore, the well-defined cavity within the prisms allowed encapsulation of pyridine-based ligands and fullerene derivatives, which led to a remarkable guest tuning of the O production.
Supramolecular nanocapsule 1⋅(BArF)8 is able to sequentially and selectively entrap recently discovered U2@C80 and unprecedented Sc2CU@C80, simply by soaking crystals of 1⋅(BArF)8 in a toluene solution of arc‐produced soot. These species, selectively and stepwise absorbed by 1⋅(BArF)8, are easily released, obtaining highly pure fractions of U2@C80 and Sc2CU@C80 in one step. Sc2CU@C80 represents the first example of a mixed metal actinide‐based endohedral metallofullerene (EMF). Remarkably, the host–guest studies revealed that 1⋅(BArF)8 is able to discriminate EMFs with the same carbon cage but with different encapsulated cluster and computational studies provide support for these observations.
A self-assembled Cu -based nanocapsule enables efficient and straightforward isolation of Sc N@C from arc-processed raw soot. The newly designed Cu -based supramolecular nanocapsule 5⋅(OTf) was used to effectively entrap fullerenes and endohedral metallofullerenes (EMFs) with different affinities depending on their size and shape. Moreover, we took advantage of the sharply different entrapment abilities of the 5⋅(OTf) cage in the solid state versus in solution to encapsulate all the species with the exception of Sc N@C (both I and D isomers), which remains pure in solution. HPLC quantification determined that up to 85 % of the total Sc N@C content in the initial mixture was recovered in very high purity (>99.5 %). The complete release of the encapsulated species with an orthogonal solvent-washing strategy regenerates 5⋅(OTf) ready to be re-used. This approach opens new opportunities for EMFs purification.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.