Stimuli‐Responsive Topological Transformation of a Molecular Borromean Ring via Controlled Oxidation of Thioether Moieties

Abstract

A Cp*‐Rh based D‐shaped binuclear metallacycle and a template‐free molecular Borromean ring (BR) were obtained in high yield using the semi‐rigid thioether dipyridyl ligand 1,4‐bis[(pyridin‐4‐ylthio)methyl]benzene (Bptmb). The topological transformation from a binuclear metallacycle and a BR to tetranuclear metallacycles was realized via the controlled oxidation of thioethers. The strategy used in this work can be regarded as a new form of stimuli‐responsive post‐synthesis modification (PSM).

An Adaptable Water-Soluble Molecular Boat for Selective Separation of Phenanthrene from Isomeric Anthracene

“…Purposeful incorporation of a flexible group in the ligand core would make the internal cavity flexible and in turn adaptive for perfect fit of the guest molecules. Flexible ligands can yield aesthetically beautiful architectures and more importantly can yield applications that are otherwise not achievable by rigid donors. , Flexible cavities can encapsulate the guest molecule by changing the cavity size for better fitting of the incoming guest like the induced fit model in biological systems …”

Coordination-directed self-assembly of nano-cages: metal ion-change, ligand-extending, shape-control and transdermal drug delivery

“…As shown in Scheme 2, a variety of supramolecular coordination assemblies, from a 1D chain structure to 2D (M = Cu) polygons and 3D (M = Cu, Na) nano-cages, have been constructed by using metal ions to tune their cage sizes for potential applications. [40][41][42][43][44][45][46][47][48][49][50][51] The sodium or potassium salt of LH3tzdc was added to a solution of [Cp*RhCl 2 ] 2 in MeOH. The reaction mixture was stirred with AgOTf for 12 h, and then sixfold pyridyl donor ligands (L1 to L5) with the metal salt Cu(NO 3 ) 2 $3H 2 O were added to the mixture, and ve kinds of [8Rh + 4Cu]-6L cages were obtained respectively.…”

Chiral Metal–Organic Framework Nanostructures for Chiral Channel-Dependent Enantioselective Sensing

“…34−37 In recent years, chiral MOFs have been widely used as basic nanomaterials for enantioselective sensing. 38,39 For example, the design and preparation of chiral polycrystalline MOF-808 membranes were first reported by Dan Zhao et al 40 at the National University of Singapore, who achieved chirality through postsynthesis modification of chiral amino acids. In 2019, Han et al demonstrated that chiral and luminescent functional motifs can be introduced into an anionic zinc-based MOF by simple cation exchange, resulting in chiral luminescent bifunctional nanomaterials.…”

“…Therefore, chiral MOFs can be designed by the following methods, such as synthesis by chiral ligands or isomers, synthesis by using template molecules action, direct synthesis with achiral ligands, and postsynthesis modification. − In recent years, CMOFs with the properties of predesired structures/functions, high stability, and porosity have attracted much attention in various application fields such as gas adsorption/separation, sensing, catalysis, drug delivery, or energy storage . Among these advantages, the most notable is their highly tunable and modifiable structures, which can be precisely constructed through the selection of well-designed frameworks to meet the requirements of advanced applications. − In recent years, chiral MOFs have been widely used as basic nanomaterials for enantioselective sensing. , For example, the design and preparation of chiral polycrystalline MOF-808 membranes were first reported by Dan Zhao et al at the National University of Singapore, who achieved chirality through postsynthesis modification of chiral amino acids. In 2019, Han et al demonstrated that chiral and luminescent functional motifs can be introduced into an anionic zinc-based MOF by simple cation exchange, resulting in chiral luminescent bifunctional nanomaterials .…”