Reversible Activation of Water by an Air- and Moisture-Stable Frustrated Rhodium Nitrogen Lewis Pair

[Cp*Rh(κ³N,N′,P- L )][SbF₆] (Cp*=C₅Me₅), bearing a guanidine-derived phosphano ligand L , behaves as a “dormant” frustrated Lewis pair and activates H₂ and H₂O in a reversible manner. When D₂O is employed, a facile H/D exchange at the Cp* ring takes place through sequential C(sp³)−H bond activation.     

Synthesis of μ2-Oxo-Bridged Iron(III) Tetraphenylporphyrin–Spacer–Nitroxide Dimers and their Structural and Dynamics Characterization by using EPR and MD Simulations

Iron(III) porphyrins have the propensity to form μ₂-oxo-dimers, the structures of which resemble two wheels on an axle. Whereas their crystal structure is known, their solution structure and internal dynamics is not. In the present work, the structure and dynamics of such dimers were studied by means of electron paramagnetic resonance (EPR) spectroscopy and quantum chemistry based molecular dynamics (MD) simulations by using the semiempirical tight-binding method (GFN-xTB). To enable EPR investigation of the dimers, a nitroxide was attached to each of the tetraphenylporphyrin cores through a linear and a bent linker. The inter-nitroxide distance distributions within the dimers were determined by continuous-wave (cw)-EPR and pulsed electron–electron double resonance (PELDOR or DEER) experiments and, with the help of MD, interpreted in terms of the rotation of the porphyrin planes with respect to each other around the Fe–O–Fe axis. It was found that such rotation is restricted to the four registers defined by the phenyl substituents. Within the registers, the rotation angle swings between 30° and 60° in the proximal and between 125° and 145° in the distal register. With EPR, all four angles were found to be equally populated, whereas the 30° and 145° angles are strongly favored to the expense of the 60° and 125° angles in the MD simulation. In either case, the internal dynamics of these dimers thus resemble the motion of a step motor.     

Synthesis,crystal structure and magnetic properties of a new tri‐nuclear iron (II,III) complex,a precursor for the preparation of superparamagnetic Fe3O4 nanoparticles applicable in the removal of Cd2+

This study reports the structural and spectroscopic characterization of a novel metal organic compound formulated as [Fe (bpy)₃] [Fe (dipic)₂]₂.7H₂O ( 1 ) (dipic = pyridine‐2,6‐dicarboxylate and bpy = 2,2^′‐bipyridine). 1 was investigated by elemental analysis, FT‐IR spectroscopy, powder X‐ray diffraction and single crystal X‐ray diffraction (SC‐XRD), which revealed a triclinic structure of expected composition. Thermal degradation of 1 was also investigated. Complex 1 was used as a precursor to prepare superparamagnetic nanoparticles of Fe₃O₄ by thermal analysis. The obtained Fe₃O₄ was characterized by Fourier transformed infrared spectroscopy (FT‐IR), powder X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Fe₃O₄ nanoparticles were used as a nano‐adsorbent to remove Cd²⁺ from water at room temperature. The results showed that this nano‐adsorbent is effective in removing Cd²⁺ from contaminated water sources, and that the maximal effectivity of adsorption occurs at pH = 6. Magnetic measurements of complex 1 and Fe₃O₄ nanoparticles at room temperature revealed paramagnetic and superparamagnetic behavior, respectively.     

Effects of substituents on bridging ligands on the single‐molecule magnet properties of Zn2Dy2 cluster complexes

Two new Zn₂Dy₂ complexes were constructed from Zn (II) salen‐type Schiff base complex fragment and 2,6‐pyridinedimethanol (H₂pdm) or its Br‐substituted analogue (4‐bromopyridine‐2,6‐diyl)dimethanol (H₂Brpdm); their molecular formulas are [Zn₂Dy₂(L)₂(pdm)₂(MeOH)₂](ClO₄)₂ [ 1 , H₂L = N, N′‐ bis(3‐methoxysalicylidene)‐1,3‐diaminopropane] and [Zn₂Dy₂(L)₂(Brpdm)₂(MeOH)₂](ClO₄)₂ [ 2 ], the Dy (III) ions of which have a NO₇ triangular dodecahedral coordination sphere. The two complexes show not only ferromagnetic interaction but also field‐induced single‐molecule magnet (SMM) behavior, which are rare Dy (III)‐containing cluster complexes with the NO₇ triangular dodecahedral coordination sphere that can show good magnetic relaxation. The energy barrier value of complex 2 is higher than those of complex 1 and the Dy (III) complexes with the DyNO₇ triangular dodecahedral coordination configuration reported in the literature.     

基于利他偏好的电商供应链最优决策与契约协调

构建了由一个占主导地位的电商平台和一个处于跟随地位的制造商组成的Stackelberg主从博弈模型,研究了电商平台有无利他偏好时电商供应链的最优决策和契约协调问题,并通过数值算例验证了本文的主要结论.研究表明:电商平台的利他偏好行为能够促使自身服务水平提高、正向影响制造商的最优销售价格并削弱自身利润.但电商平台的让利行为能够提高制造商的利润水平、缓和供应链冲突并改善供应链整体绩效."销售佣金比例+服务成本共担"契约能够完美的协调电商供应链,使双方最优利润获得帕累托改进,从而保证电商平台有足够的激励执行利他偏好行为.另外,进一步分析发现电商平台的利他偏好正向影响制造商支付给电商平台的固定技术服务费、制造商占有的电商供应链利润份额和服务成本分担比例,负向影响自身的销售佣金比例.     

一种新型双吡啶悬臂Mn(Ⅱ)配合物的合成、晶体结构及DNA结合能力研究

通过3,3′-((乙烷-1,2-二基双(2-甲基吡啶杂氮二基)双(亚甲基))双(2-羟基-5-甲基苯甲醛)与2-羟基-1,3-丙二胺的缩合反应得到一种具有双吡啶悬臂的双核锰配合物。通过X射线单晶衍射确定了该配合物结构,结果显示其分子式为[Mn₂(C₃₇H₄₃N₆O₆)]·(ClO₄)₂。该配合物属于单斜晶系,P2₁/c空间群,晶胞参数为:a=1.096 50(19) nm, b=1.419 5(3) nm, c=3.109 4(5) nm, β=108.153(5)°。进一步分析表明两个二价锰离子分别与(N_amine)₂(N_imine)₂O₃和(N_imine)₂O₄体系配位,它们与配位原子形成的几何构型分别是十面体和扭曲的八面体。两个中心锰离子距离为0.331 6 nm,由酚氧原子和醋酸根共同桥联。另外,本文也利用伏安法和黏度法对该配合物与小牛胸腺DNA的结合能力进行研究,实验结果表明它们之间的结合方式为弱的插入作用。     

Explosive synchronization in a mobile network in the presence of a positive feedback mechanism

Synchronization is a process that describes the coherent dynamics of a large ensemble of interacting units.The study of explosive synchronization transition attracts considerable attention.Here,I report the explosive transition within the framework of a mobile network,while each oscillator is controlled by global-order parameters of the system.Using numerical simulation,I find that the explosive synchronization(ES)transition behavior can be controlled by simply adjusting the fraction of controlled oscillators.The influences of some parameters on explosive synchronization are studied.Moreover,due to the presence of the positive feedback mechanism,I prevent the occurrence of the synchronization of continuous-phase transition and make phase transition of the system a first-order phase transition accompanied by a hysteresis loop.