Browse
Submit Data
Databases
API
Help

Dataset Information

22 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Playing with the weakest supramolecular interactions in a 3D crystalline hexakis[60]fullerene induces control over hydrogenation selectivity.

ABSTRACT: Weak forces can play an essential role in chemical reactions. Controlling such subtle forces in reorganization processes by applying thermal or chemical stimuli represents a novel synthetic strategy and one of the main targets in supramolecular chemistry. Actually, to separate the different supramolecular contributions to the stability of the 3D assemblies is still a major challenge. Therefore, a clear differentiation of these contributions would help in understanding the intrinsic nature as well as the chemical reactivity of supramolecular ensembles. In the present work, a controlled reorganization of an hexakis[60]fullerene-based molecular compound purely governed by the weakest van der Waals interactions known, i.e. the dihydrogen interaction - usually called sticky fingers - is illustrated. This pre-reorganization of the hexakis[60]fullerene under mild conditions allows a further selective hydrogenation of the crystalline material via hydrazine vapors exposure. This unique two-step transformation process is monitored by single-crystal to single-crystal diffraction (SCSC) which allows the direct observation of the molecular movements in the lattice and the subsequent solid-gas hydrogenation reaction.

SUBMITTER: Fernandez-Bartolome E

PROVIDER: S-EPMC8246095 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Supramolecular frameworks based on [60]fullerene hexakisadducts.

Project description:[60]Fullerene hexakisadducts possessing 12 carboxylic acid side chains form crystalline hydrogen-bonding frameworks in the solid state. Depending on the length of the linker between the reactive sites and the malonate units, the distance of the [60]fullerene nodes and thereby the spacing of the frameworks can be controlled and for the most elongated derivative, continuous channels are obtained within the structure. Stability, structural integrity and porosity of the material were investigated by powder X-ray diffraction, thermogravimetry and sorption measurements.

| S-EPMC5238557 | biostudies-literature

Hexakis-adducts of [60]fullerene as molecular scaffolds of polynuclear spin-crossover molecules.

Project description:A family of hexakis-substituted [60]fullerene adducts endowed with the well-known tridentate 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligand for spin-crossover (SCO) systems has been designed and synthesized. It has been experimentally and theoretically demonstrated that these molecular scaffolds are able to form polynuclear SCO complexes in solution. UV-vis and fluorescence spectroscopy studies have allowed monitoring of the formation of up to six Fe(ii)-bpp SCO complexes. In addition, DFT calculations have been performed to model the different complexation environments and simulate their electronic properties. The complexes retain SCO properties in the solid state exhibiting both thermal- and photoinduced spin transitions, as confirmed by temperature-dependent magnetic susceptibility and Raman spectroscopy measurements. The synthesis of these complexes demonstrates that [60]fullerene hexakis-adducts are excellent and versatile platforms to develop polynuclear SCO systems in which a fullerene core is surrounded by a SCO molecular shell.

| S-EPMC8178998 | biostudies-literature

A 3D Peptide/[60]Fullerene Hybrid for Multivalent Recognition.

Project description:Fully substituted peptide/[60]fullerene hexakis-adducts offer an excellent opportunity for multivalent protein recognition. In contrast to monofunctionalized fullerene hybrids, peptide/[60]fullerene hexakis-adducts display multiple copies of a peptide in close spatial proximity and in the three dimensions of space. High affinity peptide binders for almost any target can be currently identified by in vitro evolution techniques, often providing synthetically simpler alternatives to natural ligands. However, despite the potential of peptide/[60]fullerene hexakis-adducts, these promising conjugates have not been reported to date. Here we present a synthetic strategy for the construction of 3D multivalent hybrids that are able to bind with high affinity the E-selectin. The here synthesized fully substituted peptide/[60]fullerene hybrids and their multivalent recognition of natural receptors constitute a proof of principle for their future application as functional biocompatible materials.

| S-EPMC9826239 | biostudies-literature

A retro Baeyer-Villiger reaction: electrochemical reduction of [60]fullerene-fused lactones to [60]fullerene-fused ketones.

Project description:A highly efficient electrochemical reduction of [60]fullerene-fused lactones to [60]fullerene-fused ketones, a formal process of retro Baeyer-Villiger reaction, has been achieved for the first time. The electrochemically generated dianionic [60]fullerene-fused lactones can be transformed into [60]fullerene-fused ketones in the presence of acetic acid in 85-91% yields. Control experiments have been performed to elucidate the reaction mechanism. The products have been characterized with spectroscopic data and single-crystal X-ray analysis. Moreover, the electrochemical properties have also been investigated.

| S-EPMC6427942 | biostudies-literature

Squeezing formaldehyde into C<sub>60</sub> fullerene.

Project description:The cavity inside fullerene C60 provides a highly symmetric and inert environment for housing atoms and small molecules. Here we report the encapsulation of formaldehyde inside C60 by molecular surgery, yielding the supermolecular complex CH2O@C60, despite the 4.4 Å van der Waals length of CH2O exceeding the 3.7 Å internal diameter of C60. The presence of CH2O significantly reduces the cage HOMO-LUMO gap. Nuclear spin-spin couplings are observed between the fullerene host and the formaldehyde guest. The rapid spin-lattice relaxation of the formaldehyde 13C nuclei is attributed to a dominant spin-rotation mechanism. Despite being squeezed so tightly, the encapsulated formaldehyde molecules rotate freely about their long axes even at cryogenic temperatures, allowing observation of the ortho-to-para spin isomer conversion by infrared spectroscopy. The particle in a box nature of the system is demonstrated by the observation of two quantised translational modes in the cryogenic THz spectra.

| S-EPMC10957948 | biostudies-literature

Ligand scaffold optimization of a supramolecular hydrogenation catalyst: Analyzing the influence of key structural subunits on reactivity and selectivity.

Project description:Results are reported for the catalytic asymmetric hydrogenation of two prototypical substrates with a series of more than 150 closely related supramolecular catalysts differing in only their ligand/catalyst scaffold. These modular catalysts are constructed from four subunits and vary widely in their reactivity (no reaction to quantitative yield) and enantioselectivity (racemic to 96% ee). Analysis of the ligand/catalyst scaffold optimization data reveals how each subunit contributes to the effectiveness of the modular supramolecular catalyst. The results suggest that a balance between key elements of rigidity and flexibility is required for the successful catalysts and, moreover, that this balance is required to enable effective fine-tuning via catalyst scaffold optimization.

| S-EPMC3601680 | biostudies-literature

Base-iodine-promoted metal-catalyst-free reactions of [60]fullerene with β-keto esters for the selective formation of [60]fullerene derivatives.

Project description:In this study, methanofullerenes and 2',3'-dihydrofuran C60 derivatives were selectively synthesized in high yields via the reactions of C60 with β-keto esters under mild conditions by controlling the addition sequence and molar ratio of iodine and base. The structures of the products were determined by spectroscopic characterization. Moreover, a possible reaction mechanism for the selective formation of fullerene derivatives was proposed.

| S-EPMC9055150 | biostudies-literature

Fabrication of supramolecular cyclodextrin-fullerene nonwovens by electrospinning.

Project description:Direct electrospinning of small molecules has great potential to fabricate a new class of fiber materials because this approach realizes the creation of various functional materials through the numerous molecular combinations. In this paper, we demonstrate a proof-of-concept to fabricate supramolecular fiber materials composed of cyclodextrin (CD)-fullerene inclusion complexes by electrospinning. Similar to the molecular state of fullerenes in solution, the resulting fibers include molecularly-dispersed fullerenes. We believe such a concept could be expanded to diverse host-guest complexes, opening up supramolecular solid materials science and engineering.

| S-EPMC6334797 | biostudies-literature

Enhanced Thermoelectricity in Metal-[60]Fullerene-Graphene Molecular Junctions.

Project description:The thermoelectric properties of molecular junctions consisting of a metal Pt electrode contacting [60]fullerene derivatives covalently bound to a graphene electrode have been studied by using a conducting-probe atomic force microscope (c-AFM). The [60]fullerene derivatives are covalently linked to the graphene via two meta-connected phenyl rings, two para-connected phenyl rings, or a single phenyl ring. We find that the magnitude of the Seebeck coefficient is up to nine times larger than that of Au-C60-Pt molecular junctions. Moreover, the sign of the thermopower can be either positive or negative depending on the details of the binding geometry and on the local value of the Fermi energy. Our results demonstrate the potential of using graphene electrodes for controlling and enhancing the thermoelectric properties of molecular junctions and confirm the outstanding performance of [60]fullerene derivatives.

| S-EPMC10103166 | biostudies-literature

Reactions of [60]fullerene with alkynes promoted by OH.

Project description:In the current work, the reactions of [60]fullerene with alkynes promoted by OH- (base) are addressed. The treatment of C60 with alkynes in the presence of TBAOH produces alkynylation products (R-C60-H) with high selectivity in o-DCB at 100 °C. Plausible reaction mechanisms were proposed. This work provides a convenient and environmental friendly method for the functionalization of fullerenes.

| S-EPMC9087709 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data