Introducing functionalities into the interior of metal-organic cage complexes can confer properties and utilities ( catalysis, separation, drug delivery, and guest recognition) that are distinct from those of unfunctionalized cages. Endohedral functionalization of such cage molecules, for decades, has largely relied on modifying their organic linkers to covalently append targeted functional groups to the interior surface. We herein introduce an effective coordination method to bring in functionalities at the metal sites instead, for a set of polyhedral cages where the nodes are formed polyoxovanadate clusters, [V O(OCH)(μ-SO)(COO)]. Replacing the central sulfates of these hexavanadate clusters with more strongly coordinating phosphonate groups allows the installation of functionalities within the cage cavities. Organophosphonates with phenyl, biphenyl, and terphenyl tails were examined for internalization. Depending on the size/shape of the cavities, small phosphonates can fit into the molecular containers whereas larger ones inhibit or transform the framework architecture, whereby the first non-cage complex was isolated from a reaction that otherwise would lead to entropically favored regular polyhedra cages. The results highlight the complex and dynamic nature of the self-assembly process involving polyoxometalates and the scope of molecular variety accessible by the introduction of endo functional groups.
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http://dx.doi.org/10.1039/d1sc01243f | DOI Listing |
J Am Chem Soc
December 2024
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.
Nano Lett
December 2024
Center for High Pressure Science (CHiPS), State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, Hebei 066004, China.
The endohedral fullerene LuN@C was examined using in situ high-pressure measurements, which included electrical transport, Fourier-transform infrared spectroscopy, and Raman spectroscopy, in combination with theoretical calculations. LuN@C was found to undergo a reversible n- to p-type conversion at ∼8.9 GPa.
View Article and Find Full Text PDFJ Comput Chem
January 2025
College of Electronic and Electrical Engineering, Henan Normal University, Xinxiang, China.
Phys Chem Chem Phys
December 2024
Department of Chemistry, University of Massachusetts Lowell, Lowell, MA 01854, USA.
The electrostatic potential (ESP) has been widely used to visualize electrostatic interactions about a molecule. However, electrostatic effects are often insufficient for capturing the entirety of an interaction or a reaction of interest. In this investigation, intermolecular interaction potential maps (IMIPs), constructed from the potentials derived from energy decomposition analysis (EDA) using density functional theory, were developed and applied to provide unique insight into molecular interactions and reactivity.
View Article and Find Full Text PDFSci Rep
October 2024
Department of Pure and Applied Chemistry, University of Calabar, PMB 1115, Calabar, Nigeria.
Nanostructured materials have gained significant attention as anode material in rechargeable lithium-ion batteries due to their large surface-to-volume ratio and efficient lithium-ion intercalation. Herein, we systematically investigated the electronic and electrochemical performance of pristine and endohedral doped (O and Se) GeC and SiC nanocages as a prospective negative electrode for lithium-ion batteries using high-level density functional theory at the DFT/B3LYP-GD3(BJ)/6-311 + G(d, p)/GEN/LanL2DZ level of theory. Key findings from frontier molecular orbital (FMO) and density of states (DOS) revealed that endohedral doping of the studied nanocages with O and Se tremendously enhances their electrical conductivity.
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