Recent progress in atomically precise silver nanocluster-assembled materials.

In the dynamic landscape of nanotechnology, atomically precise silver nanoclusters (Ag NCs) have emerged as a novel and promising category of materials with their fascinating properties and enormous potential. However, recent research endeavors have surged towards stabilizing Ag-based NCs, leading to innovative strategies like connecting cluster nodes with organic linkers to construct hierarchical structures, thus forming Ag-based cluster-assembled materials (CAMs). This approach not only enhances structural stability, but also unveils unprecedented opportunities for CAMs, overcoming the limitations of individual Ag NCs. In this context, this review delves into the captivating realm of atomically precise nitrogen-based ligand bonded Ag(I)-based CAMs, providing insights into synthetic strategies, structure-property relationships, and diverse applications. We navigate the challenges and advancements in integrating Ag(I) cluster nodes, bound by argentophilic interactions, into highly connected periodic frameworks with different dimensionalities using nitrogen-based linkers. Despite the inherent diversity among cluster nodes, Ag(I) CAMs demonstrate promising potential in sensing, catalysis, bio-imaging, and device fabrication, which all are discussed in this review. Therefore, gaining insight into the silver nanocluster assembly process will offer valuable information, which can enlighten the readers on the design and advancement of Ag(I) CAMs for state-of-the-art applications.

A "heat set" Zr-Diimide based Fibrous Metallogel: Multiresponsive Sensor, Column-based Dye Separation, and Iodine Sequestration.

Sensing and monitoring hazardous contaminants in water and radioactive iodine sequestration is pivotal due to their detrimental impact on biological ecosystems. In this context, herein, a water stable zirconium-diimide based metallogel (Zr@MG) with fibrous columnar morphology is accomplished through the "heat set" method. The presence of diimide linkage with long aromatic chain manifests active luminescence properties in the linker as well as in the supramolecular framework structure. The as-synthesized Zr@MG xerogel can selectively detectCr2O72- (LOD = 0.52 ppm) and 2,4,6-trinitrophenol (TNP) (LOD = 80.2 ppb) in the aqueous medium. The Zr@MG paper strip-based detection for Cr2O72- and nitro explosive makes this metallogel reliable and an attractive luminescent sensor for practical use. Moreover, a column-based dye separation experiment was performed to show selective capture of positively charged methylene blue (MB) dye with 98 % separation efficiency from the mixture of two dyes. Also, the Zr@MG xerogel showed effective iodine sequestration from the vapor phase (232 wt%).

A Wide Bandgap Semiconducting Magnesium Hydrogel: Moisture Harvest, Iodine Sequestration, and Resistive Switching.

Water harvesting from the ubiquitous moisture is pivotal for delivering fresh water to earth's arid/semiarid regions, and sequestration of iodine from the solution is crucial for environmental safety due to its severe effect on human metabolic processes. In this context, herein, a multifunctional supramolecular metallohydrogel (Mg@TAEA) is synthesized through direct mixing of magnesium nitrate hexahydrate and the low molecular weight gelator tris(2-aminoethyl)amine. Electron microscopy reveals that Mg@TAEA is sculptured in vertically grown well-oriented micrometer-sized flakes. The porous crystalline material (52 m2/g) was found to be an efficacious host matrix for water harvesting from moisture (847 mg/g). Mg@TAEA shows effective (513 mg/g) iodine sequestration from solution and adsorption of carbon dioxide (15 mg/g). The wide bandgap semiconducting Mg@TAEA (3.6 eV) material is a potential candidate for building memory devices, and the Ion/Ioff ratio of the device based on the indium tin oxide (ITO)/Mg@TAEA/Ag heterostructure was found to be ∼62. We further extended our work by analyzing the charge transport properties of the system and found space charge limited conduction (SCLC) and trap-filled SCLC to be responsible for the nonlinear transport behavior observed in the device.

A thixotropic supramolecular metallogel with a 2D sheet morphology: iodine sequestration and column based dye separation.

Sequestration of hazardous radioactive iodine and dye separation to reduce industrial waste through reutilization is pivotal for environmental safety. In this regard, herein, the synthesis of a new waterborne ultrasensitive supramolecular metallogel (Mg@DEOA) with a 2D sheet morphology is accomplished through direct mixing of a low molecular weight gelator diethanolamine and magnesium nitrate hexahydrate. This porous metallogel (180 m2 g-1) exhibits thixotropic properties and is injectable. The material was found to be an effective (587 mg g-1) host matrix for iodine sequestration from solution. Moreover, the Mg@DEOA xerogel was used to efficiently remove rhodamine B from a mixture of dyes with high separation factors through a xerogel packed column and as an adsorbent material for water-soluble dyes and CO. This column based application demonstrated by the metallogel could be useful for practical industrial dye-separation.

Tunable Metallogels Based on Bifunctional Ligands: Precursor Metallogels, Spinel Oxides, Dye and CO2 Adsorption.

A semisolid gel material is a gift of serendipity via various chemical interactions, and metal incorporation (metallogels) imparts diverse functional properties. In this work, we have synthesized four metallogels from tetrapodal and hexapodal carboxylic acid/amide-based low-molecular-weight gelators with Ni(II) and Cu(II) salts. These metallogels can be tuned to be a low-temperature precursor of porous spinel oxides. These xerogels exhibit impressive water soluble dye and carbon dioxide adsorption, which coupled with the tunability and facile synthesis of porous spinel oxides underscores their potential in environmental remediation and energy applications.

Ligand assisted electrocatalytic water oxidation by a copper(ii) complex in neutral phosphate buffer.

The electrocatalytic water oxidation activity of a copper(ii) complex, 1, [Cu(L1H)(L1)(OH2)](ClO4), with a redox active aryl oxime ligand, L1H [L1H = 1-(pyridin-2-yl) ethanone oxime] has been investigated. Complex 1 shows a remarkably high turnover frequency of ∼100 s-1 in neutral phosphate buffer at about 675 mV overpotential with ∼94% faradaic efficiency. Electrochemical analysis suggests the involvement of a ligand moiety in a proton-coupled-electron-transfer (PCET) step during the catalytic cycle of complex 1, which in turn provides a route for accumulation of high oxidizing equivalents at the reaction center.