RhIII-Catalyzed Direct Heteroarylation of Unactivated C(sp3)-H with N-Heteroaryl Boronates.

Disclosed herein is a rhodium(III)-catalyzed direct heteroarylation reaction between unactivated aliphatic C(sp3)-H bonds in 2-alkylpyridines and heteroaryl organoboron reagents. This catalytic protocol is compatible with various heterocyclic boronates containing ortho- and meta-pyridine, pyrazoles, furan, and quinoline with strong coordination capability. The achievement of this methodology provides an efficient route to build new C(sp3)-heteroaryl bonds.

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

A catalytic protocol for the Cp*RhIII-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 ortho- and meta-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 CoN4 sites and wrapped Co2 P nanoclusters as dual-active centers (Co2 P/CoN4 @NSC-500). A crystalline {CoII 2 } coordination cluster divided by periphery second organic layers is well-designed to realize delocalized dispersion before calcination. The optimal Co2 P/CoN4 @NSC-500 executes excellent 4e- ORR activity surpassing the benchmark Pt/C. Theoretical calculation results reveal that the CoN4 sites and Co2 P nanoclusters can synergistically quicken the formation of *OOH on Co sites. The rechargeable Zn-air battery (ZAB) assembled by Co2 P/CoN4 @NSC-500 delivers ultralong cycling stability over 1742 hours (3484 cycles) under 5 mA cm-2 and can light up a 2.4 V LED bulb for ≈264 hours, evidencing the promising practical application potentials in portable devices.

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

An efficient RhIII-catalyzed strategy for constructing aryl-heteroaryl derivatives with removable ketoxime ether auxiliaries via 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.

Real-Time Fluorescent Monitoring of Kinetically Controlled Supramolecular Self-Assembly of Atom-Precise Cu8 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 CuI nanocluster [Cu8 (t BuC6 H4 S)8 (PPh3 )4 ] (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 polymorphism and different emission properties of Cu NCs aggregates were successfully captured, allowing the structure-optical property relationship to be established. More importantly, the utilization of a mathematical "permutation and combination" ideology by introducing a heterogeneous luminescent agent of a carbon dot (CD) to Cu8a aggregates enriches the "visualization" fluorescence window, which offers great potential in real time application for optical sensing of materials.

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 {MnII6MnIII4} nanocage (SD/Mn10) which is protected by both acyclic trimer [Si3] and cyclic tetramer [Si4]. Serendipitous capture of atmospheric CO2 as a µ5-carbonate anion placed at the center supports the formation of the cluster. The magnetic analysis reveals the strong antiferromagnetic interactions between Mn ions. Moreover, the drop-casting film of SD/Mn10 shows photoelectric activity indicating its great potential as a semiconductor for photoelectric conversion applications.

Nanocage-Based N-Rich Metal-Organic Framework for Luminescence Sensing toward Fe3+ and Cu2+ 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 (LCU-103) has been constructed and characterized. It is a 2-fold interpenetrating structure built from N-rich {Zn6(dttz)4} nanocages extended by N-donor ligand Hdpa [H3dttz = 4,5-di(1H-tetrazol-5-yl)-2H-1,2,3-triazole; Hdpa = 4,4'-dipyridylamine]. Notably, LCU-103 contains abundant N functional sites anchoring on both the windows of nanocages and the inner channels of the framework that can interact with metal ions and then recognize them. As a result, it can serve as a luminescent sensing material for detecting trace amounts of Fe3+ and Cu2+ ions with low limits of detection (LODs) of 1.45 and 1.66 µM, respectively, through a luminescent quenching mechanism. Meanwhile, LCU-103 as a LMOF sensor exhibits several advantages such as high sensitivity, appropriate selectivity (for Fe3+ in H2O), recycling stability, and fast response times in N,N-dimethylformamide. Moreover, LCU-103 also displays good luminescent quenching activity toward Fe3+ in H2O and a simulated 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid biological system with low LODs of 1.51 and 1.52 µM, respectively. LCU-103 test papers were further prepared to offer easy and real-time detection of Fe3+ and Cu2+ ions. Importantly, when density functional theory calculations and multiple experimental evidence, including X-ray photoelectron spectroscopy, UV-vis absorption, luminescence decay lifetimes, and quantum efficiencies, are combined, a preferred N-donor site and possible weak interaction sensing mechanism is also proposed to elucidate the quenching effect.

Simultaneous Trapping of C2 H2 and C2 H6 from a Ternary Mixture of C2 H2 /C2 H4 /C2 H6 in a Robust Metal-Organic Framework for the Purification of C2 H4.

The removal of C2 H2 and C2 H6 from C2 H4 streams is of great significance for feedstock purification to produce polyethylene and other commodity chemicals but the simultaneous adsorption of C2 H6 and C2 H2 over C2 H4 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 C2 H2 and C2 H6 over C2 H4 . Breakthrough experiments show that TJT-100 can be used as an adsorbent for high-performance purification of C2 H4 from a ternary mixture of C2 H2 /C2 H4 /C2 H6 (0.5:99:0.5) to afford a C2 H4 purity greater than 99.997 %, beyond that required for ethylene polymerization. Computational studies reveal that the uncoordinated carboxylate oxygen atoms and coordinated water molecules pointing towards the pore can trap C2 H2 and C2 H6 through the formation of multiple C-H⋅⋅⋅O electrostatic interactions, while the corresponding C2 H4 -framework interaction is unfavorable.

Ferromagnetic Polarization: The Quantum Picture of Switching On/Off Single-Molecule Magnetism.

The mixed 3d-4f pentanuclear complex (Bu4N)[Mn(III)4Y(III)(shi)4(OAc)4(CH3OH)4]·CH3OH·H2O (1) (H3shi = salicylhydroxamic acid) was synthesized by the direct reaction of Y(NO3)3·6H2O, Mn(OAc)2·4H2O, and H3shi. When an additional ligand, (NHBu3)3[W(CN)8]·2H2O, was added, the mixed 3d-4f-5d hexanuclear complex (Et4N)5[Mn(III)4Y(III)(shi)4(OAc)4W(V)(CN)8](WO4)0.5 (2) was obtained. X-ray crystallographic analysis shows that the 3d-4f complex 1 represents a 12-metallacrown-4 (12-MC-4) structure, in which the metallacrown ring [Mn-N-O]4 connection captures one Y(III) ion with four bridging acetate anions, completing the eight-coordinated environment around Y(III) ion, while four methanol molecules each coordinate to the Mn(III) ions on the other side of the Y(III) ion. After octacyanotungstate is introduced, the [W(V)(CN)8] group substitutes for four methanol molecules of 1 to form complex 2. Magnetic studies indicate the overall antiferromagnetic coupling present within the MC ring of complex 1. However, interestingly, the dominant ferromagnetic coupling between Mn(III) ions was observed in complex 2. A susceptibility analysis shows that the natural spin alignments in 12-MC-4 metallacrowns are tuned from overall antiferromagnetic to dominant ferromagnetic fashions by magnetic coupling between Mn(III) ions and the W(V) ion. Complex 1 [Mn(III)4Y(III)] retains an S = 0 ground state, and complex 2 [Mn(III)4Y(III)W(V)] shows obvious single-molecule magnet (SMM) behavior with an ST = 11/2 ground state, respectively, before and after introduction of the octacyanotungstate group. The spin frustration geometrical structure constructed by four Mn(III) ions and one W(V) ion was considered as the key factor for switching on the SMM properties of the 12-MC-4 system.

Two novel lead(II) complexes of 2-(hydroxymethyl)pyridine: a threefold diamondoid supramolecular network based on Pb4O4 cores and a two-dimensional (4,4) network based on Pb2O2 units.

Reactions of 2-(hydroxymethyl)pyridine (Hhmp) with PbCl2 and Pb(NO3)2 at room temperature led to the formation of two novel compounds, namely tetrakis[µ3-(pyridin-2-yl)methanolato]-tetrahedro-tetrakis[chloridolead(II)], [Pb4(C6H6NO)4Cl4], (I), and poly[(µ2-nitrato)[µ2-(pyridin-2-yl)methanolato]lead(II)], [Pb(C6H6NO)(NO3)]n, (II). Compound (I) exhibits a tetranuclear Pb4O4 cubane structure, which is connected through π-π stacking interactions between the pyridine groups of the (pyridin-2-yl)methanolate (hmp(-)) ligands and through C-H···Cl interactions to form an interesting threefold diamondoid network. Compound (II) possesses two-dimensional (4,4)-sql topology based on a Pb2O2 unit, which is further extended into a three-dimensional supramolecular network through π-π stacking interactions between adjacent pyridine rings and through C-H···O interactions between the pyridine C atoms of the hmp(-) ligands and the nitrate anions.

Solvent-Induced Isomeric Cu13 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) (Cu13a and Cu13b) containing highly similar Cu13 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. Due to the charge transition from chlorine to the copper core (X(Cl)M(Cu)CT), the molecular oxygen activation of Cu13a showed higher singlet oxygen (1O2) and lower superoxide radical (O2•-) yields compared to those of Cu13b, which gives it better catalytic selectivity for the 1O2 involved selective oxidation of sulfides. The present work not only offers a controllable strategy for the rational design and synthesis of quasi-structurally isomeric Cu NCs but also provides a pathway to boost catalytic selectivity by a halogen to metal core charge transition.

Stepwise Assembly of Ag42 Nanocalices Based on a MoVI-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 Ag42 nanoclusters (Ag42c-Ag42f) based on MoVI-anchored p-tert-butylthiacalix[4]arene (H4TC4A) as a metalloligand (hereafter named MoO3-TC4A). X-ray crystallography demonstrates that they are similar C3-symmetric silver-organic nanocalices capped by six MoO3-TC4A metalloligands, which are evenly distributed up and down the base of 42 silver atoms. These nanoclusters can be disassembled to six bowl-shaped [Ag11(MoO3-TC4A)(RS)3] secondary building units (SBUs, R = Et or nPr), which are fused together in a face-sharing fashion surrounding Cl- or Br- as a central anion template. The electrospray mass spectrometry (ESI-MS) indicates their high stabilities in solution and verifies the formation of the MoO3-TC4A metalloligand, thereby rationalizing the overall stepwise assembly process for them. Moreover, Ag42c shows lower cytotoxicity and better activity against the HepG-2 cell line than MCF-7 and BGC-823. These results not only exemplify the effectiveness of a thiacalix[4]arene-based metalloligand in the assembly of silver nanoclusters but also give us profound insight about the step-by-step assembly process in silver nanoclusters.

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

A RhIII-catalyzed C(sp2)-H N-heteroarylation and esterification cascade of aryl carboxylic acids with N-heteroaromatic boronates and 1,2-dichloroethane in a one-pot synthesis has been disclosed. The strong coordinating ability of ortho- and meta-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.

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(sp2)-H heteroarylation/esterification reaction of acrylic acid is disclosed herein for the first time. This catalytic protocol tolerates various α-substituted, ß-substituted, and α, ß-disubstituted acrylic acids as well as heteroaromatic boronates well. The resulting 3,4-dihydro-2H-pyran-6-carboxylic acid derivative 3r 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.

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. The N/C-900 material was fabricated by pyrolysis of a designed crystal MOF LCU-104, which exhibits a graceful two-fold interpenetrating structural feature of N-rich nanocages {Zn6(dttz)4} linked through an N-donor ligand bpp (H3dttz = 4,5-di(1H-tetrazol-5-yl)-2H-1,2,3-triazole, bpp = 1,3-bis(4-pyridyl)propane). The features of LCU-104 combine high N content (35.1%), interpenetration, and explosive characteristics, which endow the derived N/C material with optimized N-doping for tuning its chemical and electronic structure, a suitably thicker wall to enhance its stability, and a vesicle-like structure to improve its porosity. As an anode material for LIBs, N/C-900 delivers a highly reversible capacity of ca. 734 mA h g-1 at a large current density of 1 A g-1 until the 2000th cycle, revealing its ultralong cycle stability and excellent rate capability. The unique structure and preferential interaction between abundant pyridinic N active sites and Li atoms are responsible for the improved excellent lithium storage capacity and durability performances of the anode according to analysis of the results of computational modeling.

Nuclearity enlargement from [PW9O34@Ag51] to [(PW9O34)2@Ag72] 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 [PW9O34@Ag51] (SD/Ag51b) fuse to a double-pod [(PW9O34)2@Ag72] 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 44-sql layer (SD/Ag72a) with bipy and a 3D pcu framework (SD/Ag72c) with pi-bipy. The PW9O349- retains its structure during the cluster fusion and cluster-based network formation. Although the two processes, stripping of an Ag-ligands interface followed by fusion, and polymerization, are difficult to envisage, electrospray ionization mass spectrometry provides enough evidences for such a proposal to be made. Through this example, we expect the structural transformation to become a powerful method for synthesizing silver nanoclusters and their infinite networks, and to evolve from trial-and-error to rational.

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 P- and M-single stranded helical superstructures spontaneously assembled from R- and S-Au8c individual nanoclusters, respectively, upon selecting chiral BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthalene) and hydrophilic o-H2MBA (o-mercaptobenzoic acid) as protective ligands to induce chirality and facilitate the formation of helixes. Structural analysis reveals that the chirality of the Au8c individual nanoclusters is derived from the homochiral ligands and the inherently chiral Au8 metallic kernel, which was further corroborated by experimental and computational investigations. More importantly, driven by the O-H⋯O interactions between (HCO3 -)2 dimers and achiral o-HMBA- ligands, R/S-Au8c individual nanoclusters can assemble into helical superstructures in a highly ordered crystal packing. Electrospray ionization (ESI) and collision-induced dissociation (CID) mass spectrometry of Au8c confirm the hydrogen-bonded dimer of Au8c individual nanoclusters in solution, illustrating that the insertion of (HCO3 -)2 dimers plays a crucial role in the assembly of helical superstructures in the crystalline state. This work not only demonstrates an effective strategy to construct cluster-based helical superstructures at the atomic level, but also provides visual and reliable experimental evidence for understanding the formation mechanism of helical superstructures.

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

RhIII-catalyzed sp2 C-H cross-coupling of acrylamides with organoboron reactants has been accomplished using a commercially available N-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.

RhIII-Catalyzed Direct Heteroarylation of C(sp3)-H and C(sp2)-H Bonds in Heterocycles with N-Heteroaromatic Boronates.

Herein, we disclose a RhIII-catalyzed heteroarylation of C(sp3)-H and C(sp2)-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. The direct heteroarylation method could supply potential application in terms of the synthesis of drug molecules with multiple heterocycles.

A Co-MOF-derived Co9S8@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 Co9S8 nanoparticles embedded in a porous N,S-dual doped carbon composite (abbr. Co9S8@NS-C-900) were fabricated by the pyrolysis of a single crystal Co-MOF assisted with thiourea. Due to the synergistic benefit of combining Co9S8 nanoparticles with N,S-dual doped carbon, the composite showed efficient HER electrocatalytic activities and long-term durability in an alkaline solution. It shows a small overpotential of -86.4 mV at a current density of 10.0 mA cm-2, a small Tafel slope of 81.1 mV dec-1, and a large exchange current density (J 0) of 0.40 mA cm-2, which are comparable to those of Pt/C. More importantly, due to the protection of Co9S8 nanoparticles by the N,S-dual doped carbon shell, the Co9S8@NS-C-900 catalyst displays excellent long-term durability. There is almost no decay in HER activities after 1000 potential cycles or it retains 99.5% of the initial current after 48 h.