Rh-Catalyzed Direct Heteroarylation of Unactivated C(sp)-H with -Heteroaryl Boronates.

Disclosed herein is a rhodium(III)-catalyzed direct heteroarylation reaction between unactivated aliphatic C(sp)-H bonds in 2-alkylpyridines and heteroaryl organoboron reagents. This catalytic protocol is compatible with various heterocyclic boronates containing - and -pyridine, pyrazoles, furan, and quinoline with strong coordination capability. The achievement of this methodology provides an efficient route to build new C(sp)-heteroaryl bonds.

Rh-promoted directed C-H N-heteroarylation of 2-pyridones.

A catalytic protocol for the Cp*Rh-promoted C6-selective N-heteroarylation of 2-pyridones with N-heterocyclic boronates has been successfully developed utilizing a removable pyridine auxiliary. This system features high efficiency with mild conditions and also tolerates - and -substituted pyridines, pyrazoles, pyrimidine, non-substituted quinolines, thiophene and furan well. The easy synthetic approach could potentially be applied to construct heterocyclic drug molecules bearing 2-pyridone-heteroaryl motifs.

A "Pre-Division Metal Clusters" Strategy to Mediate Efficient Dual-Active Sites ORR Catalyst for Ultralong Rechargeable Zn-Air Battery.

To conquer the bottleneck of sluggish kinetics in cathodic oxygen reduction reaction (ORR) of metal-air batteries, catalysts with dual-active centers have stood out. Here, a "pre-division metal clusters" strategy is firstly conceived to fabricate a N,S-dual doped honeycomb-like carbon matrix inlaid with CoN sites and wrapped Co P nanoclusters as dual-active centers (Co P/CoN @NSC-500). A crystalline {Co } coordination cluster divided by periphery second organic layers is well-designed to realize delocalized dispersion before calcination.

One-Pot Construction of Heteroarylation/Esterification Products of Acrylic Acids via Iridium(III)-Catalyzed C-H Activation.

A carboxylate-assisted iridium(III)-catalyzed regioselective C(sp)-H heteroarylation/esterification reaction of acrylic acid is disclosed herein for the first time. This catalytic protocol tolerates various α-substituted, β-substituted, and α, β-disubstituted acrylic acids as well as heteroaromatic boronates well. The resulting 3,4-dihydro-2-pyran-6-carboxylic acid derivative highlighted the AIE-active luminophore with multiple emission signal properties and a high quantum yield of 28%, exhibiting the potential application of this methodology for the synthesis of nitrogen-containing organic functional materials.

Bicarbonate insertion triggered self-assembly of chiral octa-gold nanoclusters into helical superstructures in the crystalline state.

Constructing atomically precise helical superstructures of high order is an extensively pursued subject for unique aesthetic features and underlying applications. However, the construction of cluster-based helixes of well-defined architectures comes with a huge challenge owing to their intrinsic complexity in geometric structures and synthetic processes. Herein, we report a pair of unique and single stranded helical superstructures spontaneously assembled from - and -Au8c individual nanoclusters, respectively, upon selecting chiral BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthalene) and hydrophilic -HMBA (-mercaptobenzoic acid) as protective ligands to induce chirality and facilitate the formation of helixes.

Rh-Catalyzed C-H -Heteroarylation and Esterification Cascade of Carboxylic Acid with Organoboron Reagents and 1,2-Dichloroethane in One-Pot Synthesis.

A Rh-catalyzed C(sp)-H -heteroarylation and esterification cascade of aryl carboxylic acids with -heteroaromatic boronates and 1,2-dichloroethane in a one-pot synthesis has been disclosed. The strong coordinating ability of - and -substituted pyridine boronates and pyrazoles as well as unsubstituted pyrimidine allows them to serve as the coupling partners. This protocol allows late-stage modification of the key precursor of roflumilast and compounds of pharmaceutical interest, which highlights the potential application of this synthetic method.

Solvent-Induced Isomeric Cu Nanoclusters: Chlorine to Copper Charge Transfer Boosting Molecular Oxygen Activation in Sulfide Selective Oxidation.

Isomers with minimal structural dissimilarities are promising research objects to obtain a comprehensive understanding of structure-property relationships; however, comparability of isomeric structures is a prerequisite. Herein, two quasi-structurally isomeric 13-nuclei copper nanoclusters (Cu NCs) ( and ) containing highly similar Cu kernels and different arrangements of peripheral ligands were obtained using a solvent-induced strategy. The exotic chloride ion is shown to play a prominent role in inducing the selective formation of two quasi-isomers, where the comparative study to establish a structure-property relationship was realized.

Interpenetrated N-rich MOF derived vesicular N-doped carbon for high performance lithium ion battery.

High-performance lithium ion batteries (LIBs) juggling high reversible capacity, excellent rate capability and ultralong cycle stability are urgently needed for all electronic devices. Here we report employing a vesicle-like porous N-doped carbon material (abbr. N/C-900) as a highly active anode for LIBs to balance high capacity, high rate and long life.

Nuclearity enlargement from [PWO@Ag] to [(PWO)@Ag] and 2D and 3D network formation driven by bipyridines.

The structural transformations of metal nanoclusters are typically quite complex processes involving the formation and breakage of several bonds, and thus are challenging to study. Herein, we report a case where two lacunary Keggin polyoxometallate templated silver single-pods [PWO@Ag] (SD/Ag51b) fuse to a double-pod [(PWO)@Ag] by reacting with 4,4'-bipyridine (bipy) or 1,4-bis(4-pyridinylmethyl)piperazine (pi-bipy). Their crystal structures reveal the formation of a 2D 4-sql layer (SD/Ag72a) with bipy and a 3D pcu framework (SD/Ag72c) with pi-bipy.

Stepwise Assembly of Ag Nanocalices Based on a Mo-Anchored Thiacalix[4]arene Metalloligand.

Metalloligand strategy has been well recognized in the syntheses of heterometallic coordination polymers; however, such a strategy used in the assembly of silver nanoclusters is not broadly available. Herein, we report the stepwise syntheses of a family of halogen-templated Ag nanoclusters (-) based on Mo-anchored --butylthiacalix[4]arene (HTC4A) as a metalloligand (hereafter named MoO-TC4A). X-ray crystallography demonstrates that they are similar -symmetric silver-organic nanocalices capped by six MoO-TC4A metalloligands, which are evenly distributed up and down the base of 42 silver atoms.

Real-Time Fluorescent Monitoring of Kinetically Controlled Supramolecular Self-Assembly of Atom-Precise Cu Nanocluster.

Kinetically stable and long-lived intermediates are crucial in monitoring the progress and understanding of supramolecular self-assembly of diverse aggregated structures with collective functions. Herein, the complex dynamics of an atomically precise Cu nanocluster [Cu ( BuC H S) (PPh ) ] (Cu8a) is systematically investigated. Remarkably, by monitoring the aggregation-induced emission (AIE) and electron microscopy of the kinetically stable intermediates in real time, the directed self-assembly (DSA) process of Cu8a is deduced.

The synthesis of aryl-heteroaryl derivatives the Rh-catalyzed heteroarylation of arenes and heteroaromatic boronates.

An efficient Rh-catalyzed strategy for constructing aryl-heteroaryl derivatives with removable ketoxime ether auxiliaries direct C-H heteroarylation based on arenes and heteroaromatic boronates has been disclosed. This protocol could tolerate various pyridine, pyrimidine, pyrazole, thiophene, and furan heteroaromatic boronates well, providing the desired products with high reactivities and excellent regioselectivity. The easy synthetic accessibility may offer potential for application in the synthesis of heterocyclic drug molecules containing aryl-heteroaryl motifs.

A Carbonate-Templated Decanuclear Mn Nanocage with Two Different Silsesquioxane Ligands.

The mild reaction of the preorganized silsesquioxane precursor with Mn(II) acetate under ambient conditions results in a mixed-valent {MnMn} nanocage () which is protected by both acyclic trimer [Si3] and cyclic tetramer [Si4]. Serendipitous capture of atmospheric CO as a μ-carbonate anion placed at the center supports the formation of the cluster. The magnetic analysis reveals the strong antiferromagnetic interactions between Mn ions.

Rh-Catalyzed Direct Heteroarylation of C(sp)-H and C(sp)-H Bonds in Heterocycles with -Heteroaromatic Boronates.

Herein, we disclose a Rh-catalyzed heteroarylation of C(sp)-H and C(sp)-H bonds in heterocycles with organoboron reagents. This protocol displays high efficiency and excellent functional group tolerance. A range of heterocyclic boronates with strong coordinating atoms, including pyridine, pyrimidine, pyrazole, thiophene, and furan derivatives, can be extensively served as the coupling reagents.

Carboxylic acid-tuned nickel(ii) clusters: syntheses, structures, solution behaviours and magnetic properties.

Three novel cicada-like nickel(ii) clusters, formulated as [Ni(bdped)(mba)(Hdmpz)(NO)(HO)]·4MeCN (SD/Ni6b), [Ni(bdped)(tca)(Hdmpz)(MeOH)(HO)]·MeOH (SD/Ni5a) and [Ni(Hbdped)(ba)(Hdmpz)]·2NO·2MeCN (SD/Ni4a), were obtained by tuning the auxiliary carboxylic acids, where Hbdped = 1,2-bis-(3,5-dimethylpyrazol-1-yl)-ethane-1,2-diol; Hmba = 2-methylbenzoic acid; Hdmpz = 3,5-dimethyl-1H-pyrazole; Htca = 3-thiophenecarboxylic acid; and Hba = benzoic acid. The structures of SD/Ni6b, SD/Ni5a and SD/Ni4a are built from a central NiO opened cube, appending two to zero NiNO octahedra. The solution behaviours of SD/Ni6b, SD/Ni5a and SD/Ni4a were studied in detail via an ESI-MS technique and their solution stabilities were confirmed.

A Co-MOF-derived CoS@NS-C electrocatalyst for efficient hydrogen evolution reaction.

The exploitation of efficient hydrogen evolution reaction (HER) electrocatalysts has become increasingly urgent and imperative; however, it is also challenging for high-performance sustainable clean energy applications. Herein, novel CoS nanoparticles embedded in a porous N,S-dual doped carbon composite (abbr. CoS@NS-C-900) were fabricated by the pyrolysis of a single crystal Co-MOF assisted with thiourea.

Rh-Catalyzed C-H (Het)arylation/Vinylation of -2,6-Difluoroaryl Acrylamides.

Rh-catalyzed sp C-H cross-coupling of acrylamides with organoboron reactants has been accomplished using a commercially available -2,6-difluoroaryl acrylamide auxiliary. A broad range of aryl and vinyl boronates as well as a variety of heterocyclic boronates with strong coordinating ability can serve as the coupling partners. This transformation proceeds under moderate reaction conditions with excellent functional group tolerance and high regioselectivity.

Nanocage-Based N-Rich Metal-Organic Framework for Luminescence Sensing toward Fe and Cu Ions.

Luminescent metal-organic frameworks (LMOFs) as sensors showing highly efficient detection toward toxic heavy-metal ions are in high demand for human health and environmental protection. A novel nanocage-based N-rich LMOF () has been constructed and characterized. It is a 2-fold interpenetrating structure built from N-rich {Zn(dttz)} nanocages extended by N-donor ligand Hdpa [Hdttz = 4,5-di(1-tetrazol-5-yl)-2-1,2,3-triazole; Hdpa = 4,4'-dipyridylamine].

Fe-MOF-Derived Efficient ORR/OER Bifunctional Electrocatalyst for Rechargeable Zinc-Air Batteries.

The construction of an efficient oxygen reduction reaction and oxygen evolution reaction (ORR/OER) bifunctional electrocatalyst is of great significance but still remains a giant challenge for high-performance metal-air batteries. In this study, uniform FeS/FeC nanoparticles embedded in a porous N,S-dual doped carbon honeycomb-like composite ( FeS/FeC@NS-C-900) have been conveniently fabricated by pyrolysis of a single-crystal , which has a low potential gap Δ of ca. 0.

Investigating the effect of lanthanide radius and diamagnetic linkers on the framework of metallacrown complexes.

By changing the stoichiometric ratios, the one-pot reaction of the glycinehydroxamic acid (H2glyha) ligand with copper(ii) and lanthanide(iii) salts in the presence of diamagnetic [Na2{Fe(CN)5(NO)}] led to two series of isostructural complexes, which can be designated as heterotrimetallic dimeric clusters [{LnCu5(glyha)5}{Fe(CN)5(NO)}(H2O)4]2·xNO3·yH2O (x = 2, y = 11 for La (1), x = 2, y = 11 for Pr (2), and x = 2, y = 11 for Nd (3)) and heterotetrametallic coordination polymers [Na{LnCu5(glyha)5}{Fe(CN)5(NO)}2(H2O)x·yH2O]n (x = 6, y = 4 for Sm (4), x = 6, y = 0 for Gd (5), x = 6, y = 4 for Tb (6), x = 5, y = 5 Dy (7), and x = 6, y = 4 for Ho (8)). Each molecular structure contains LnIII[15-metallacrown-5] nodes and diamagnetic [Fe(CN)5(NO)]2- linkers. The resulting products demonstrate diversified structural frameworks due to the radius effect of LnIII ions and different bridging fashions of diamagnetic [Fe(CN)5(NO)]2- linkers.

Two microporous Co-MOFs with dual active sites for highly selective adsorption of CO/CH and CO/N.

Simultaneously involving abundant [NH2(CH3)2]+ cations and uncoordinated carboxylate oxygen atoms as dual active sites, two microporous CoII-MOFs (LCU-105 and LCU-106, LCU = Liaocheng University) both exhibit highly selective adsorption of CO2/CH4 and CO2/N2. GCMC theoretical simulations provide good verification of the experimental results.

Room temperature synthesis of CdS/SrTiO nanodots-on-nanocubes for efficient photocatalytic H evolution from water.

Spontaneous solar-driven water splitting to generate H with no pollution discharge is an ideal H generation approach. However, its efficiency remains far from real application owing to the poor light-harvesting and ultrafast charge recombination of photocatalysts. To address these issues, herein, we employed a novel but simple chemical bath deposition (CBD) method to construct CdS/SrTiO nanodots-on-nanocubes at room temperature (ca.

Simultaneous Trapping of C H and C H from a Ternary Mixture of C H /C H /C H in a Robust Metal-Organic Framework for the Purification of C H.

The removal of C H and C H from C H streams is of great significance for feedstock purification to produce polyethylene and other commodity chemicals but the simultaneous adsorption of C H and C H over C H from a ternary mixture has never been realized. Herein, a robust metal-organic framework, TJT-100, was designed and synthesized, which demonstrates remarkably selective adsorption of C H and C H over C H . Breakthrough experiments show that TJT-100 can be used as an adsorbent for high-performance purification of C H from a ternary mixture of C H /C H /C H (0.

Unprecedented family of heterometallic Ln[18-metallacrown-6] complexes: syntheses, structures, and magnetic properties.

Herein, a new family of Ln[18-metallacrown-6] compounds with the formula [FeOLn(tBu-sao)(OH)(MeO)(MeOH)(HO)]·6MeOH [Ln = Dy (1), Tb (2), Gd (3), and Y (4), tBu-saoH = 3,5-di-tert-butylsalicylaldoxime] was synthesized through one-pot reactions using tBu-saoH, Fe(ClO)·6HO, and Ln(NO)·6HO. The four compounds are isostructural, and the encapsulation of a Ln ion in the ring cavity of 18-metallacrown-6 (18-MC-6) was exhibited for the first time. The structural analysis shows a ship-like 18-MC-6 core with a beset lanthanide ion connecting six ring oxygen atoms (O).

Two microporous Fe-based MOFs with multiple active sites for selective gas adsorption.

Two Fe-based porous MOFs have been constructed from dimeric Fe-clusters and rod-shaped heterobimetallic {FeNa} chains as SBUs, respectively. Both of them exhibit highly selective CO adsorption over CH and N, owing to their abundant multiple active sites.