A convenient catalytic approach to synthesize straight boron nitride nanotubes using synergic nitrogen source

Straight boron nitride nanotubes (BNNTs) with pure hexagonal phase were conveniently prepared by heating the mixture of Mg(BO₂)₂ · H₂O, NH₄Cl, NaN₃ and Mg powder in an autoclave at 600 °C for 20–60 h. These BNNTs had diameters mainly ranging 30–300 nm and lengths up to 5 μm, and a majority of them had at least one closed end. Besides the traditional end tips, additional cone-like tips were frequently found to be attached on the BNNTs. The effects of temperature, reactants and the possible mechanism of the catalytic formation of the BNNTs are discussed.     

阵列式压电振子超声复合喷丸强化*

为了进一步改善超声喷丸强化质量,提升工件表面残余应力和显微硬度的均匀性,对压电振子阵列型超声喷丸强化加工系统进行了改进,提出了在强化加工过程中辅助工件往复运动的方法。对改进后的压电振子阵列型超声喷丸强化加工原理进行了阐述,分析了激振片的振动特性并进行了结构尺寸优化,应用Abaqus对工件往复运动下超声喷丸强化过程进行了仿真研究,分析了在不同的工件往复运动频率下,工件表面残余应力分布情况。实验测试了在不同喷丸强化时间及工件往复运动频率下超声喷丸强化加工质量,探究了喷丸时间和工件往复运动频率对工件表面显微硬度的影响。结果表明：在压电振子阵列型超声喷丸强化过程中辅助工件往返运动,可以有效提高工件表面残余应力和显微硬度分布的均匀性,工件表面强化质量得到提升。     

One-dimensional cyanide-bridged Cr(III)–Cu(II) complexes: synthesis,crystal structures and magnetic properties

Using two trans-dicyanidechromium(III) precursors K[Cr(bpdmb)(CN)₂] (bpdmb^2? = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate), K[Cr(bpClb)-(CN)₂] (bpClb^2? = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate) and one Cu(II) complex of a 14-membered macrocycle as ancillary organic ligand as assembling segments, two one-dimensional cyanide-bridged Cr^III–Cu^II complexes {{[Cu(cyclam)][Cr(bpdmb)(CN)₂]}ClO₄} _n ·nCH₃OH·nH₂O (1) and {{[Cu(cyclam)][Cr(bpClb)(CN)₂]}ClO₄} _n ·nCH₃OH (2) (cyclam = 1,4,8,11-tetraazacyclotetradecane) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray structure determination. Single X-ray diffraction analysis shows that their similar one-dimensional cationic single-chain structures consist of alternating units of [Cu(cyclam)]²⁺ and [Cr(bpdmb)(CN)₂]^?/[Cr(bpClb)(CN)₂]^? with free ClO₄ ^? as balancing anions. Investigations of the temperature dependences of magnetic susceptibility and the field-dependent magnetization reveal that both complexes have overall ferromagnetic coupling between the neighboring Cr(III) and Cu(II) centers through the bridging cyanide groups.     

Photoinduced Reaction of α-Bromoacetophenone with Thiosulfonate: Synthesis of β-Keto Thiosulfone

A photoinduced synthesis of β-keto thiosulfone/β-keto selenosulfone by the reaction of α-bromoacetophenone with thiosulfonate/selenosulfonate under metal-free and visible light irradiation conditions is developed. Two C−S bonds or one C−S bond and one C−Se bond were constructed simultaneously.     

One-dimensional heterobimetallic cyanide-bridged Fe(III)–Mn(II) complex: Synthesis,crystal structure,and magnetic properties

A new cyanide-bridged heterobimetallic Fe(III)–Mn(II) complex {[MnL][FebpdBrb]} [FebpdBrb]_n· 2nH₂O has been synthesized by using pyridinecarboxamide trans-dicyanideiron as the building block. The X-ray diffraction analysis has revealed the one-dimensional infinite structure of the complex consisting of the alternating [Mn(L)]²⁺ and [Fe(bpdBrb)(CN)₂]^– units forming a cyanide-bridged cationic polymeric chain, with [Fe(bpdBrb)(CN)₂]^– as the free anions. The antiferromagnetic coupling between the neighboring Fe(III) and Mn(II) ions through the bridging cyanide group has been revealed. The magnetic coupling constant has been determined as of J =–3.17 cm^–1.     

A new three‐dimensional cobalt(II) coordination polymer based on V‐shaped 3,4′‐oxydibenzoate: synthesis,crystal structure and magnetic properties

A new coordination polymer (CP), namely poly[(μ‐4,4′‐bipyridine)(μ₃‐3,4′‐oxydibenzoato)cobalt(II)], [Co(C₁₄H₈O₅)(C₁₀H₈N₂)]_n or [Co(3,4′‐obb)(4,4′‐bipy)]_n ( 1 ), was prepared by the self‐assembly of Co(NO₃)₂·6H₂O with the rarely used 3,4′‐oxydibenzoic acid (3,4′‐obbH₂) ligand and 4,4′‐bipyridine (4,4′‐bipy) under solvothermal conditions, and has been structurally characterized by elemental analysis, IR spectroscopy, single‐crystal X‐ray crystallography and powder X‐ray diffraction (PXRD). Single‐crystal X‐ray diffraction reveals that each Co^II ion is six‐coordinated by four O atoms from three 3,4′‐obb^2? ligands, of which two function as monodentate ligands and the other as a bidentate ligand, and by two N atoms from bridging 4,4′‐bipy ligands, thereby forming a distorted octahedral CoN₂O₄ coordination geometry. Adjacent crystallographically equivalent Co^II ions are bridged by the O atoms of 3,4′‐obb^2? ligands, affording an eight‐membered Co₂O₄C₂ ring which is further extended into a two‐dimensional [Co(3,4′‐obb)]_n sheet along the ab plane via 3,4′‐obb^2? functioning as a bidentate bridging ligand. The planes are interlinked into a three‐dimensional [Co(3,4′‐obb)(4,4′‐bipy)]_n network by 4,4′‐bipy ligands acting as pillars along the c axis. Magnetic investigations on CP 1 disclose an antiferromagnetic coupling within the dimeric Co₂ unit and a metamagnetic behaviour at low temperature resulting from intermolecular π–π interactions between the parallel 4,4′‐bipy ligands.     

Synthesis and characterization of three nickel(ii) carborane complexes containing nido- or closo-carborane diphosphine ligand

Three nickel(II) carborane complexes, [Ni₂(μ-Cl)₂{7,8-(PPh₂)₂-7,8-C₂B₉H₁₀}₂] (1), [Ni{7-(OPPh₂)-8-(PPh₂)-7,8-C₂B₉H₁₀}{7,8-(PPh₂)₂-7,8-C₂B₉H₁₀}] (2) and [NiBr₂{1,2-(PPh₂)₂-1,2-C₂B₁₀H₁₀}] · CH₂Cl₂ (3), have been synthesized by the reactions of 1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane with NiCl₂ · 6H₂O or NiBr₂ · 6H₂O in ethanol under different conditions, respectively. For complex 1, it could also be obtained under the solvothermal condition. All the three complexes were characterized by elemental analysis, FT-IR, ¹H and ¹³C NMR spectroscopy and X-ray structure determination. Single crystal analysis shows that the molecular symmetry of complex 1 is centrosymmetric, containing two same structure units - Ni(7,8-(PPh₂)₂-7,8-C₂B₉H₁₀) linked by two bridged-Cl atoms. The central square plane formed by the [Ni₂Cl₂] unit is almost parallel to the two side NiPP planes. For complex 2, the coordination environment of the Ni atom is a seriously distorted square-planar, in which two positions come from the chelating diphosphine ligand [7,8-(PPh₂)₂-7,8-C₂B₉H₁₀]⁻ degraded from the closo species, while the other two are occupied by an unsymmetrical chelating phosphine oxide ligand [7-(OPPh₂)-8-(PPh₂)-7,8-C₂B₉H₁₀]⁻. As for complex 3, the geometry at the Ni atom is a slightly distorted square-planar. The closo carborane diphosphine ligand 1,2-(PPh₂)₂-1,2-C₂B₁₀H₁₀ was coordinated bidentately to the metal ion through the two phosphorus atoms, and the two Br atoms are at cis position which can fulfill the four coordination mode of the metal.     

Porphyrin–Alkaline Earth MOFs with the Highest Adsorption Capacity for Methylene Blue

A series of four porphyrin–alkaline earth metal– organic frameworks [Mg(HDCPP)₂(DMF)₂]_n?(H₂O)_{7 n} ( 1 ), [Ca(HDCPP)₂(H₂O)₂]_n(DMF)_{1.5 n} ( 2 ), [Sr(DCPP)(H₂O)(DMA)]_n ( 3 ), and [Ba(DCPP)(H₂O)(DMA)]_n ( 4 ) was isolated for the first time from solvothermal reaction between metal‐free 5,15‐di(4‐ carboxyphenyl)porphyrin (H₂DCPP) and alkaline earth ions. Single‐crystal X‐ray diffraction analysis reveals the 2D and 3D supramolecular network with periodic nanosized porosity for 1 / 2 and 3 / 4 , respectively. The whole series of MOFs, in particular, compounds 1 and 2 with intrinsic low molecular formula weight, exhibit superior adsorption performance for methylene blue (MB) with excellent capture capacity as represented by the thus far highest adsorption amount of 952 mg g^?1 for 2 and good selectivity, opening a new way for the potential application of the main group metal‐based MOFs.