A new protocol is described for the conversion of heteroarene N-oxides to heteroarylphosphonates through in situ activation with bromotrichloromethane. The N-oxides of isoquinoline, quinoline, quinoxaline and 1,10-phenanthroline were fast transformed into the corresponding heteroarylphosphonates in up to 92% yield under mild conditions in the absence of solvent and metal catalysts. The good functional group tolerance, low cost, feasibility of scale up, and wide availability of reagents make this method a prominent complement to the Hirao coupling.

A metal-free one-pot synthesis of 2,3-disubstituted benzofurans is described, which allows for the reactions to be performed under ambient conditions with readily accessible propargyl alcohols and general phenols, including phenols substituted with an electron withdrawing group or a nitrogen-containing group.

An 8-connected entangled metal–organic framework has been synthesized and characterized, which not only represents the first entangled framework with coexistence of self-threading, polythreading and interpenetration, but also represents the highest connected topology presently known for self-threading and polythreading systems.

Six novel 2D metal–quinolone complexes, namely [Cd(cfH)(bpdc)]H2O (1), [M(norfH)(bpdc)]H2O (M=Cd (2) and Mn (3)), [Mn2(cfH)(odpa)(H2O)3]0.5H2O (4), [Co2(norfH)(bpta)(μ2-H2O)(H2O)2]H2O (5) and [Co3(saraH)2(Hbpta)2(H2O)4]9H2O (6) (cfH=ciprofloxacin, norfH=norfloxacin, saraH=sarafloxacin, bpdc=4,4′-biphenyldicarboxylate, odpa=4,4′-oxydiphthalate, bpta=3,3′,4,4′-biphenyltetracarboxylate) have been synthesized and characterized. Compounds 1–3 consist of 2D arm-shaped layers based on the 1D {M(COO)}nn+ chains. Compounds 4 and 5 display 2D structures based on tetranuclear manganese or cobalt clusters with (3,6)-connected kgd topology. Compound 6 exhibits a 2D bilayer structure, which represents the first example of metal–quinolone complexes with 2D bilayer structure. By inspection of the structures of 1–6, it is believed that the long aromatic polycarboxylate ligands are important for the formation of 2D metal–quinolone complexes. The magnetic properties of compounds 3–6 was studied, indicating the existence of antiferromagnetic interactions. Furthermore, the luminescent properties of compounds 1–2 are discussed.Graphical abstractSix novel 2D metal–quinolone complexes have been prepared by self-assemblies of the quinolones and metal salts in the presence of long aromatic polycarboxylates .Highlights►Compounds 1–3 consist of novel 2D arm-shaped layers based on the 1D {M(COO)}nn+ chains. ► Compounds 4 and 5 are two novel 2D layers based on tetranuclear Mn or Co clusters with kgd topology. ► Compound 6 is the first example of metal–quinolone complexes with 2D bilayer structure. ► Compounds 1–6 represent six unusual examples of 2D metal–quinolone complexes.

Bis(thiazole) pincer palladium complexes showed efficient catalytic activity for the Suzuki–Miyaura coupling of aryl halides, allowing the synthesis of biaryls with very high turnover numbers and turnover frequencies. The complexes were successfully applied in the scalable and green synthesis of the key intermediates of bioactive LUF5771 and its analogues.

Two novel NCN-pincer complex precursors bearing frameworks of 2,6-bis(oxazol-4-yl)benzene (A) and 2-(thiazol-4-yl)-6-(oxazol-4-yl)benzene (B) were synthesized. Palladations of A and B afforded two new bis(azole) pincer complexes, [(A-κ3NCN)PdBr] (1) and [(B-κ3NCN)PdBr] (2). Both complexes were fully characterized by NMR, MS, DSC-TGA and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in a noncentrosymmetric orthorhombic space group Cmc21 (No. 36, Z = 4). Complex 2 crystallizes in a centrosymmetric monoclinic space groupP21/n (No. 14, Z = 4). Despite the similarity in their chemical formulas, the structures of the two complexes are subtly different: they are built up of two-dimensional supramolecular layers with identical topology, but stacked in different sequences, i.e., the layers in complex 1 are stacked in an AAAA-type fashion, while those in complex 2 are stacked in an alternating AA−1AA−1 sequence (A denotes a layer; A−1 stands for A's inversion symmetry equivalent). In addition, the complexes showed good catalytic activity toward Mizoroki–Heck reactions.

Self-assembly of transition metal salts with long aromatic dicarboxylate ligands and N-containing ligands affords a series of entangled coordination frameworks based on different metal cores, namely [Mn4(μ2-OH2)2(sdba)4(bpp)4] (1), [Mn2(sdba)2(btb)0.5(H2O)] (2), [Mn4(sdba)4(bim)(H2O)4]·2H2O (3), [Ni(sdba)(bim)(H2O)2]·2H2O (4), [Co3(sdba)2(Hsdba)2(2,2′-bpy)2] (5) and [Ni2(bpda)2(bim)2]·H2O (6) (H2sdba = 4,4′-sulfonyldibenzoic acid, H2bpda = 4,4′-carbonyldibenzoic acid, bpp = 1,3-bis(4-pyridyl)propane, btb = 1,4-bis(1,2,4-triazol-1-yl)butane, bim = 1,4-bis(imidazol-1-yl)butane, 2,2′-bpy = 2,2′-bipyridine). Their structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra and TG analyses. Compound 1 is a peculiar 2D self-threading network containing unusual triflexural helical motifs, which can be rationalized as a 6-connected 2D 36-hxl (hexagonal lattice) net with double edges. Compound 2 represents the first example of a 2D polycatenated framework formed by 1D quadruple chains, which could be considered as formed by interconnected 1D polyrotaxane columns involving the unusual [3]rotaxane components. Compound 3 consists of two interlocked 2D cage-containing frameworks and exhibits an unusual (2D → 2D) parallel interpenetrating array with coexistence of polyrotaxane and polycatenane. Compound 4 is composed of two interpenetrating 2D loop-containing frameworks with 4-connected (2.65) topology, and it can also be considered as being constructed by interconnected parallel 1D polyrotaxane chains. Compound 5 is comprised of two identical 2D hydrogen-bonded layers with 6-connected (22.48.65) topology that are interpenetrated in a parallel fashion, resulting in a twofold interpenetrating net having both polyrotaxane and polycatenane characters. Compound 6 represents an unusual mode of interpenetration of two distinct 3D frames both with CdSO4 topology, which is still very rare in entangled systems. In addition, the magnetic properties of compounds 1, 3, 4, 5 and 6 are discussed.

A new protocol is described for the conversion of heteroarene N-oxides to heteroarylphosphonates through in situ activation with bromotrichloromethane. The N-oxides of isoquinoline, quinoline, quinoxaline and 1,10-phenanthroline were fast transformed into the corresponding heteroarylphosphonates in up to 92% yield under mild conditions in the absence of solvent and metal catalysts. The good functional group tolerance, low cost, feasibility of scale up, and wide availability of reagents make this method a prominent complement to the Hirao coupling.

Two novel NCN-pincer complex precursors bearing frameworks of 2,6-bis(oxazol-4-yl)benzene (A) and 2-(thiazol-4-yl)-6-(oxazol-4-yl)benzene (B) were synthesized. Palladations of A and B afforded two new bis(azole) pincer complexes, [(A-κ3NCN)PdBr] (1) and [(B-κ3NCN)PdBr] (2). Both complexes were fully characterized by NMR, MS, DSC-TGA and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in a noncentrosymmetric orthorhombic space group Cmc21 (No. 36, Z = 4). Complex 2 crystallizes in a centrosymmetric monoclinic space groupP21/n (No. 14, Z = 4). Despite the similarity in their chemical formulas, the structures of the two complexes are subtly different: they are built up of two-dimensional supramolecular layers with identical topology, but stacked in different sequences, i.e., the layers in complex 1 are stacked in an AAAA-type fashion, while those in complex 2 are stacked in an alternating AA−1AA−1 sequence (A denotes a layer; A−1 stands for A's inversion symmetry equivalent). In addition, the complexes showed good catalytic activity toward Mizoroki–Heck reactions.