Functional Post-Synthetic Chemistry of Metal–Organic Cages According to Molecular Architecture and Specific Geometry of Origin

Molecules, Год журнала: 2025, Номер 30(3), С. 462 - 462

Опубликована: Янв. 21, 2025

Metal–organic cages (MOCs) are discrete supramolecular entities consisting of metal nodes and organic connectors or linkers; MOCs noted for their high porosity processability. Chemically, they can be post-synthetically modified (PSM) new functional groups introduced, presenting attractive qualities, it is expected that properties will differ from those the original compound. This why highly regarded in fields biology chemistry. The present review deals with current PSM strategies used MOCs, including covalent, coordination, noncovalent methods structural benefits. main emphasis this to show what extent under circumstances a MOC designed obtain tailored geometric architecture. Although sometimes unclear when examining systems, particularizing design systematic approaches development characterization families provides insights into structure–function relationships, which guide future developments.

Язык: Английский

Self-Assembly and Dynamic Equilibrium of Trinuclear and Tetranuclear Cu(I) Supramolecules Featuring nido-Carborane-Supported N-Heterocyclic Carbene Ligands

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 8, 2025

The self-assembly of metallo-supramolecules has attracted considerable attention in recent decades. These discrete architectures are primarily driven by coordination interactions, typically involving M-N/O (Werner-type) or M-C (organometallic) bonding. However, the use M-π interactions for constructing these multinuclear complexes remains largely unexplored. In this work, we report trinuclear and tetranuclear copper(I) a combination interactions. Cu(I)-NHC were synthesized from nido-carborane-supported N-heterocyclic carbene (NHC) precursors Cu(I) ions. solution, dynamic equilibrium between species was observed, as confirmed variable-temperature NMR spectrum. Van't Hoff analysis revealed that is endothermic (ΔHeq = 53.6 kJ mol-1) entropically (ΔSeq 158 J mol-1 K-1). solid-state structures both forms elucidated through single-crystal XRD analysis. Density functional theory calculations showed Cu-CNHC bonds relatively weak (∼100 mol-1, approximately one-third strength typical bonds). This attributed to strong Coulombic attraction positively charged negatively nido-carborane ligands (M-π interactions), which significantly reduces bond neutral NHC moieties (M-C bonding).

Язык: Английский

Post-modification-induced supramolecular transformation of Hopf link to macrocycle

Chinese Chemical Letters, Год журнала: 2024, Номер unknown, С. 110684 - 110684

Опубликована: Ноя. 1, 2024

Язык: Английский