Dual Capture of Iodine and Methyl Iodide Using Nonporous Nitrogen-Enriched Palladium(II) Assemblies DOI

Raghunath Singha,

Rajesh Pradhan,

Paritosh K. De

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: June 3, 2025

The increasing reliance on nuclear energy amid fossil fuel depletion has intensified the demand for effective materials to capture and store radioactive species. Among these, molecular iodine methyl iodide present serious environmental health risks due their volatility persistence in waste. Herein, four nonporous self-assembled metallo-supramolecular assemblies (C1-C4) containing nitrogen-enriched cores (pyridyl, pyrimidine, or phenazine units) with distinct cavity sizes were investigated potential simultaneous of both organic iodide. In vapor phase, achieved exceptional uptake up 3.03 g g-1 at 75 °C, n-hexane solution, capacities reached 493.5 mg g-1, highlighting materials' efficiency across different phases facilitated by electron-pair interactions. Additionally, these exhibited excellent performance capturing vapor, adsorption as high 1.2 via methylation reactions. proved be robust reusable, maintaining efficacy over least five cycles without significant degradation. This work presents first report an N-heteroatom functionalization approach design recyclable coordination safe efficient storage iodide, contributing mitigation energy-associated risks.

Language: Английский

Template and Solid-State-Assisted Assembly of an M9L6 Expanded Coordination Cage for Medium-Sized Molecule Encapsulation DOI Creative Commons
Kenta Iizuka, Hiroki Takezawa, Makoto Fujita

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(47), P. 32311 - 32316

Published: Nov. 18, 2024

The M

Language: Английский

Citations

4
Formation of a Pd16 Molecular Basket Architecture of Reduced Symmetry and Angular Deviation in a Fluorenone Scaffold to Govern the Host–Guest Chemistry of Pd6 Trifacial Tubes DOI Creative Commons

M.L. Aggarwal,

Ranit Banerjee, Neal Hickey

et al.

JACS Au, Journal Year: 2025, Volume and Issue: 5(5), P. 2368 - 2378

Published: May 9, 2025

The employment of flexible ligands with significant conformational freedom in coordination-driven self-assembly enables the formation unique and intricate structures. In this study, such a fluorenone-appended ligand (L1) sterically demanding acceptor, [Pd-(tmed)-(ONO2)2] (M1), generated new molecular basket architecture, (M1) 16 8 (B), featuring large hollow cavity. B possesses an unusual twisted architecture low symmetry, consisting Pd-(II) centers arranged as four tetrahedra connected by eight ligands, representing structurally complex system reminiscent biological architectures. Designing entropically disfavored, architectures reduced symmetry is challenging but desirable, since they can act ideal models to study complicated natural systems. host-guest property supramolecular hosts governed confined cavities noncovalent interactions, which are dictated angular disposition coordination sites. To explore this, fluorenone scaffold was used synthesize two other tetradentate (L2 L3) that differed spatial distributions their vectors. these [Pd-(en)-(ONO2)2] (M2) resulted water-soluble 6 (L1/L2/L3) 3 trifacial tubes different geometries varying internal cavity dimensions. These variations further altered orientation carbonyl groups within cavities, thereby modulating guest binding abilities highlighting importance tailoring for specific binding.

Language: Английский

Citations

0
Design and Synthesis of a Cluster-Based Supramolecular Reaction Pump for the Efficient Catalysis of Amination Reactions DOI
Yun‐Hu Deng, Brendan F. Abrahams, Jian‐Ping Lang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 16, 2025

Although discrete self-assembled cage compounds with single-metal centers mimicking natural bioreactors for catalysis have been extensively investigated, studies on those multimetal active centers, i.e., cluster (CACs), less explored. Herein, we present the design and synthesis of a novel cluster-based supramolecular reaction pump (CSRP-1) featuring four CACs that facilitate catalysis. CSRP-1 holds cationic tetrahedral structure, comprising WS3Cu3 clusters, each positioned at one vertex interconnected by dipyridyl linkers. Substrates, including aryl iodides or primary secondary amines, enter cavity replacing N,N-dimethylformamide through weak Cu···I/N interactions. This leverages coordinatively unsaturated Cu within CAC to activate substrates, resulting in efficient catalytic amination. works like dynamic pump, upon completion reaction, amine product is expelled from cavity, allowing cycle repeat maintained efficiency. Theoretical calculations complement experimental findings, providing key insights into mechanism synergistic role clusters work offers new paradigm broad applicability various organic reactions.

Language: Английский

Citations

0
Dual Capture of Iodine and Methyl Iodide Using Nonporous Nitrogen-Enriched Palladium(II) Assemblies DOI

Raghunath Singha,

Rajesh Pradhan,

Paritosh K. De

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: June 3, 2025

The increasing reliance on nuclear energy amid fossil fuel depletion has intensified the demand for effective materials to capture and store radioactive species. Among these, molecular iodine methyl iodide present serious environmental health risks due their volatility persistence in waste. Herein, four nonporous self-assembled metallo-supramolecular assemblies (C1-C4) containing nitrogen-enriched cores (pyridyl, pyrimidine, or phenazine units) with distinct cavity sizes were investigated potential simultaneous of both organic iodide. In vapor phase, achieved exceptional uptake up 3.03 g g-1 at 75 °C, n-hexane solution, capacities reached 493.5 mg g-1, highlighting materials' efficiency across different phases facilitated by electron-pair interactions. Additionally, these exhibited excellent performance capturing vapor, adsorption as high 1.2 via methylation reactions. proved be robust reusable, maintaining efficacy over least five cycles without significant degradation. This work presents first report an N-heteroatom functionalization approach design recyclable coordination safe efficient storage iodide, contributing mitigation energy-associated risks.

Language: Английский

Citations

0