A corannulene-bis-N-imidazolium salt was used for the synthesis of two corannulene-bis-N-heterocyclic carbenes of dirhodium(i) complexes of formula (corannulene-di-NHC)[RhCl(COD)] and (corannulene-di-NHC)[RhCl(CO)]. Both complexes were characterized by spectroscopic techniques, and the electron-donating properties of the corannulene-di-NHC ligand were studied by means of infrared spectroscopy and cyclic voltammetry. The complex (corannulene-di-NHC)[RhCl(COD)] was used for the encapsulation of fullerenes C and C, generating host-guest complexes with 2 : 1 stoichiometry, as evidenced by H NMR and ITC titrations. Then, a tetra-rhodium(i) metallo-rectangle supported by two corannulene-bis-imidazolylidene ligands and two cofacial 4,4'-bipyridine ligands was prepared and characterized. This metallobox is capable of quantitatively encapsulating fullerenes C and C, forming complexes that are highly stable even at high temperatures. The molecular structure of the metallobox with encapsulated C reveals a perfect size and shape complementarity that benefits from the concave-convex π-π interaction between the polyaromatic surfaces of the host and the guest.
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http://dx.doi.org/10.1039/d4sc03661a | DOI Listing |
J Am Chem Soc
January 2025
College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, Jiangsu 215123, P. R. China.
A thorium-carbon double bond that corresponds to the sum of theoretical covalent double bond radii has long been sought after in the study of actinide-ligand multiple bonding as a synthetic target. However, the stabilization of this chemical bond remains a great challenge to date, in part because of a relatively poor energetic matching between 5f-/6d- orbitals of thorium and the 2s-/2p- frontier orbitals of carbon. Herein, we report the successful synthesis of a thorium-carbon double bond in a carbon-bridged actinide-transition metal cluster, i.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Key Laboratory of Bioorganic Phosphorous and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, China.
Zigzag aromatic hydrocarbon belts, ultrashort segments of zigzag carbon nanotubes, have been fascinating in the chemistry community for more than a half century because of their aesthetically appealing molecular nanostructures and tantalizing applications. Precise introduction of heteroatoms of distinct electronegativity and electronic configuration can create various heterocyclic aromatic nanobelts with novel physical and chemical properties. Here, we report the synthesis of unprecedented N-doped zigzag-type aromatic belts, belt[]pyrrole[]pyridines ( = 6-8), from multiple intramolecular C-C homocoupling reactions of readily available azacalix[](3,5-dibromopyridine)s.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Metal cluster fullerenes are a class of molecular nanomaterials with complex structures and novel properties. An in-depth study of their formation mechanism is a key topic for developing new high-yield synthesis methods and promoting the practical application of such molecular nanomaterials. To elucidate the formation mechanism of ScN@C, a representative sub-class of metal cluster fullerenes, this study developed a ReaxFF force field parameter set CNSc.
View Article and Find Full Text PDFOrg Lett
January 2025
GIR MIOMeT, IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, Valladolid E47011, Spain.
A method to synthesize cofacial dimeric porphyrins bearing eight corannulene units has been developed. It relies on the stability of octahedral CO-capped Ru(II) complexes linked by N-donor ligands. This specific arrangement provides an optimal scaffold to accommodate fullerenes by imposing corannulene groups at a precise distance and relative orientation.
View Article and Find Full Text PDFJ Mol Model
December 2024
Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario, L8S 4M1, Canada.
Context: In this work, we have studied different properties of a series of fullerenes, from C to C by confining hydrogen molecule inside their cavity. The compression of the hydrogen molecule upon encapsulation is evidenced by its altered bond length, while a slight expansion of the fullerene cages due to H confinement is also noted. The chemical reactivity parameters of both the empty and H confined fullerenes are computed, alongside an examination of the energy components through energy decomposition analysis.
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