Luminescent Hydride-Free [Cu7(SC5H9)7(PPh3)3] Nanocluster: Facilitating Highly Selective C-C Bond Formation.

Amidst burgeoning interest, atomically precise copper nanoclusters (Cu NCs) have emerged as a remarkable class of nanomaterials distinguished by their unparalleled reactivity. Nonetheless, the synthesis of hydride-free Cu NCs and their role as stable catalysts remain infrequently explored. Here, we introduce a facile synthetic approach to fabricate a hydride-free [Cu7(SC5H9)7(PPh3)3] (Cu7) NC and delineate its photophysical properties intertwined with their structural configuration. Moreover, the utilization of its photophysical properties in a photoinduced C-C coupling reaction demonstrates remarkable specificity toward cross-coupling products with high yields. The combined experimental and theoretical investigation reveals a nonradical mechanistic pathway distinct from its counterparts, offering promising prospects for designing hydride-free Cu NC catalysts in the future and unveiling the selectivity of the hydride-free [Cu7(SC5H9)7(PPh3)3] NC in photoinduced Sonogashira C-C coupling through a polar reaction pathway.

Covalent Organic Frameworks: Cutting-Edge Materials for Carbon Dioxide Capture and Water Harvesting from Air.

The implacable rise of carbon dioxide (CO2 ) concentration in the atmosphere and acute water stress are one of the central challenges of our time. Present-day chemistry is strongly inclined towards more sustainable solutions. Covalent organic frameworks (COFs), attributable to their structural designability with atomic precision, functionalizable chemical environment and robust extended architectures, have demonstrated promising performances in CO2 trapping and water harvesting from air. In this Review, we discuss the major developments in this field as well as sketch out the opportunities and shortcomings that remain over large-scale COF synthesis, device engineering, and long-term performance in real environments.

Five Novel Silver-Based Coordination Polymers as Photoluminescent Sensing Platforms for the Detection of Nitrobenzene.

Nitrobenzene (NB) is a highly toxic chemical and a cause for concern to human health and the environment. Hence, it is worth designing new efficient and robust sensing platforms for NB. In this study, we present three newly synthesized luminescent silver cluster-based coordination polymers, {[Ag10 (StBu)6 (CF3 COO)4 (hpbt)] (DMAc)2 (CH3 CN)2 }n (hpbt=N,N,N',N'N",N"-hexa(pyridine-4-yl)benzene-1,3,5-triamine), [Ag12 (StBu)6 (CF3 COO)6 (bpva)3 ]n (bpva=9,10-Bis(2-(pyridin-4-yl)vinyl)anthracene), and {[Ag12 (StBu)6 (CF3 COO)6 (bpb)(DMAc)2 (H2 O)2 ] (DMAc)2 }n (bpb=1,4-Bis(4-pyridyl)benzene) composed of Ag10 , Ag12 and Ag12 cluster cores, respectively, connected by multidentate pyridine linkers. In addition, two new luminescent polymorphic silver(I)-based coordination polymers, [Ag(CF3 COO)(dpa)]n (dpa=9,10-di(4-pyridyl)anthracene) referred to as Agdpa (H) and Agdpa (R), where H and R denote hexagon- and rod-like crystal shapes, respectively, have been prepared. The coordination polymers exhibit highly sensitive luminescence quenching effects to NB, attributed to the π-π stacking interactions between the polymers and NB as well as the electron-withdrawing character of NB.

Record Ultralarge-Pores, Low Density Three-Dimensional Covalent Organic Framework for Controlled Drug Delivery.

The unique structural characteristics of three-dimensional (3D) covalent organic frameworks (COFs) like high surface areas, interconnected pore system and readily accessible active sites render them promising platforms for a wide set of functional applications. Albeit promising, the reticular construction of 3D COFs with large pores is a very demanding task owing to the formation of interpenetrated frameworks. Herein we report the designed synthesis of a 3D non-interpenetrated stp net COF, namely TUS-64, with the largest pore size of all 3D COFs (47 Å) and record-low density (0.106 g cm-3 ) by reticulating a 6-connected triptycene-based linker with a 4-connected porphyrin-based linker. Characterized with a highly interconnected mesoporous scaffold and good stability, TUS-64 shows efficient drug loading and controlled release for five different drugs in simulated body fluid environment, demonstrating the competency of TUS-64 as drug nanocarriers.

A silver cluster-assembled material as a matrix for enzyme immobilization towards a highly efficient biocatalyst.

Silver cluster-assembled materials (SCAMs) epitomize well-defined extended crystalline frameworks that combine the ingenious designability at the atomic/molecular level and high structural robustness. They have captivated the interest of the scientific fraternity because of their modular construction which enables to systematically tailor their functions, and their capacity to not only inherit the characteristics of component building units but also introduce their uniqueness in endowing the final material with extraordinary properties. Herein, we demonstrate the synthesis of a novel (3,6)-connected two-dimensional (2D) SCAM [Ag12(StBu)6(CF3COO)6(THIT)6]n (described as TUS 5, THIT = 2,4,6-tri(1H-imidazol-1-yl)-1,3,5-triazine) composed of Ag12 cluster nodes and tritopic imidazolyl linkers. We have leveraged, for the first time, this precisely architected extended SCAM structure as a support matrix for enzyme immobilization. The electrostatic attraction between the negatively charged amano lipase PS and positively charged TUS 5 as well as the surface hydrophobicity of TUS 5 catered to great binding of lipase onto the TUS 5 matrix, in addition to boosting the activity of lipase via interfacial activation. Capitalizing on the cooperative benefits of organic and inorganic support matrices wherein organic supports impart with cost-efficiency, biocompatibility, and improved enzyme stability and reusability and inorganic supports confer high thermal, mechanical and microbial resistance, we have utilized the immobilized lipase on TUS 5 SCAM (lipase@TUS 5) for the kinetic resolution of (R,S)-1-phenylethanol by transesterification reaction. Importantly, lipase@TUS 5 could attain appreciably higher conversion into (R)-1-phenylethyl acetate, besides featuring superior thermal stability, solvent tolerance and recyclability, over the native lipase.

Synthesis and luminescence properties of two silver cluster-assembled materials for selective Fe3+ sensing.

Silver cluster-assembled materials (SCAMs) are emerging light-emitting materials with molecular-level structural designability and unique photophysical properties. Nevertheless, the widespread application scope of these materials is severely curtailed by their dissimilar structural architecture upon immersing in different solvent media. In this work, we report the designed synthesis of two unprecedented (4.6)-connected three-dimensional (3D) luminescent SCAMs, [Ag12(StBu)6(CF3COO)6(TPEPE)6]n (denoted as TUS 1), TPEPE = 1,1,2,2-tetrakis(4-(pyridin-4-ylethynyl)phenyl)ethene and [Ag12(StBu)6(CF3COO)6(TPVPE)6]n (denoted as TUS 2), TPVPE = 1,1,2,2-tetrakis(4-((E)-2-(pyridin-4-yl)vinyl)phenyl)ethene, composed of an Ag12 cluster core connected by quadridentate pyridine linkers. Attributed to their exceptional fluorescence properties with absolute quantum yield (QY) up to 9.7% and excellent chemical stability in a wide range of solvent polarity, a highly sensitive assay for detecting Fe3+ in aqueous medium is developed with promising detection limits of 0.05 and 0.86 nM L-1 for TUS 1 and TUS 2 respectively, comparable to the standard. Furthermore, the competency of these materials to detect Fe3+ in real water samples reveals their potential application in environmental monitoring and assessment.

A new two-dimensional luminescent Ag12 cluster-assembled material and its catalytic activity for reduction of hexacyanoferrate(III).

Silver cluster-assembled materials (SCAMs) have garnered significant interest as promising platforms for different functional explorations. Their atomically precise structures, intriguing chemical/physical properties, and remarkable luminescent capabilities make them highly appealing. However, the properties of these materials are primarily determined by their structural architecture, which is heavily influenced by the linker molecules used in their assembly. The choice of linker molecules plays a pivotal role in shaping the structural characteristics and ultimately determining the unique properties of SCAMs. To this end, the first SCAM with an intriguing (3,6)-connected kgd topology, [Ag12(StBu)6(CF3COO)6(TPBTC)6]n (termed TUS 3), TPBTC = benzene-1,3,5-tricarboxylic acid tris-pyridin-4-ylamide, has been synthesized by reticulating C6-symmetric Ag12 cluster cores with C3-symmetric tripodal pyridine linkers. Due to the structutural architecture of the linker molecule, TUS 3 posseses a luminescent porous framework structure where each two-dimensional (2D) layers are non-covalently linked with each other to form a three dimensional (3D) framework and ultimately offers uniaxial open channels. The compact mesoporous structural architecture not only gives the excellent surface area but also offers impressive stability of this material even in water medium. Taking advantage of these properties, TUS 3 shows brilliant catalytic activity in the reduction of hexacyanoferrate(III) using sodium borohydride in aqueous solutions.

Nested Keplerian architecture of [Cu58H20(SPr)36(PPh3)8]2+ nanoclusters.

This article explores the challenges in synthesizing highly symmetric Cu(I)-thiolate nanoclusters and reports a nested Keplerian architecture of [Cu58H20(SPr)36(PPh3)8]2+ (Pr = CH2CH2CH3). The structure is made up of five concentric polyhedra of Cu(I) atoms, which create enough space to accommodate five ligand shells all within a range of 2 nm. This fascinating structural architecture is also linked to the unique photoluminescence properties of the nanoclusters.

Three-Dimensional Covalent Organic Framework with scu-c Topology for Drug Delivery.

Three-dimensional (3D) covalent organic frameworks (COFs) exemplify a new generation of crystalline extended solids with intriguing structures and unprecedented porosity. Notwithstanding substantial scope, the reticular synthesis of 3D COFs from pre-designed building units leading to new network topologies yet remains a demanding task owing to the shortage of 3D building units and inadequate reversibility of the linkages between the building units. In this work, by linking a tetragonal prism (8-connected) node with a square planar (4-connected) node, we report the first 3D COF with scu-c topology. The new COF, namely, TUS-84, features a two-fold interpenetrated structure with well-defined porosity and a Brunauer-Emmett-Teller surface area of 679 m2 g-1. In drug delivery applications, TUS-84 shows efficient drug loading and sustained release profile.