3D Covalent Organic Framework with "the" Topology.

Discovery of new topology covalent organic frameworks (COFs) is a mainstay in reticular chemistry and materials research because it not only serves as a stepwise guide to the designed construction of covalent-organic architectures but also helps to comprehend function from structural design point-of-view. Proceeding on this track, the first 3D COF, TUS-38, with the topology is constructed by reticulating a planar triangular 3-c node of D3h symmetry with a tetragonal prism 8-c node of D2h symmetry via [3 + 8] reversible imine condensation reaction. TUS-38 represents a twofold interpenetrated multidirectional pore network with a high degree of crystallinity and structural integrity. Interestingly, stemming from the nitrogen-rich s-triazine rings with electron-deficient character and ─C â• N─ linkages composing the TUS-38 framework that benefit to the charge-transfer and hence dipole-dipole electrostatic interactions between the framework and iodine in addition to exclusive topological characteristics of the exotic the net, TUS-38 achieves an exemplary capacity for iodine vapor uptake reaching 6.3 g g-1. Recyclability studies evidence that TUS-38 can be reused at least five times retaining 95% of its initial adsorption capacity; while density functional theory (DFT) calculations have heightened the understanding of the interactions between iodine molecules and the framework.

Metal Nanoclusters as a Superior Polysulfides Immobilizer toward Highly Stable Lithium-Sulfur Batteries.

Due to their high designability, unique geometric and electronic structures, and surface coordination chemistry, atomically precise metal nanoclusters are an emerging class of functional nanomaterials at the forefront of materials research. However, the current research on metal nanoclusters is mainly fundamental, and their practical applications are still uncharted. The surface binding properties and redox activity of Au24 Pt(PET)18 (PET: phenylethanethiolate, SCH2 CH2 Ph) nanoclusters are herein harnessed as an high-efficiency electrocatalyst for the anchoring and rapid conversion of lithium polysulfides in lithium-sulfur batteries (LSBs). Au24 Pt(PET)18 @G composites are prepared by using the large specific surface area, high porosity, and conductive network of graphene (G) for the construction of battery separator that can inhibit polysulfide shuttle and accelerate electrochemical kinetics. Resultantly, the LSB using a Au24 Pt(PET)18 @G-based separator presents a high reversible specific capacity of 1535.4 mA h g-1 for the first cycle at 0.2 A g-1 and a rate capability of 887 mA h g-1 at 5 A g-1 . After 1000 cycles at 5 A g-1 , the capacity is 558.5 mA h g-1 . This study is a significant step toward the application of metal nanoclusters as optimal electrocatalysts for LSBs and other sustainable energy storage systems.

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.

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.

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.

Silver cluster-assembled materials for label-free DNA detection.

Herein, we report two newly synthesized silver cluster-assembled materials (SCAMs), [Ag14(StBu)10(CF3COO)4(bpa)2]n (bpa = 1,2-bis(4-pyridyl)acetylene) and [Ag12(StBu)6(CF3COO)6(bpeb)3]n (bpeb = 1,4-bis(pyridin-4-ylethynyl)benzene) composed of Ag14 and Ag12 chalcogenolate cluster cores, respectively, bridged by acetylenic bispyridine linkers. The linker structures and electrostatic interaction between positively charged SCAMs and negatively charged DNA confer the SCAMs with the ability to suppress the high background fluorescence of single-stranded (ss) DNA probes with SYBR Green I nucleic acid stain, leading to high signal-to-noise ratio for label-free target DNA detection.

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.

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.