Temperature-controlled Hydrothermal Synthesis of Copper(Ⅰ or Ⅱ) Coordination Polymers via a Variety of Copper Coordination Modes

Two 1D coordination polymers Cu2I（C6N3H4）2（1） and CuⅡ（C6N3H4）2·H2O（2） based on benzotriazole（Bta） were hydrothermally synthesized by controlling the crystallization temperature.Single-crystal X-ray diffraction（XRD） analyses reveal that compound 1 is a 1D tubular structure constructed from two types of 1D chains {―Cu―N=N―N―} n,where the Cu（I） ions adopt linear,triangular,and tetrahedral coordination modes to connect two types of Bta ligands via π-π interaction inside the tubular-like chain.For compound 2,the Cu（Ⅱ） ions assume a quadrilateral coordination mode linking to the Bta ligands to give 1D straight chains,which stacks through π-π interactions to construct a 2D layer structure.Further characterizations including elemental analyses,infrared IR spectra,thermogravimetric（TG） analyses and luminescence properties have been done.

A New Europium Coordination Compound Supported by 4,6-Dibenzoylisophthalic Acid Ligands

A unique metal-organic framework（MOF） [Eu_2（L）_3（phen）_2]_n（1, H_2L = 4,6-dibenzoylisophthalic acid, phen = 1,10-phenanthroline） has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray analysis, elemental analyses, powder X-ray diffraction, TGA measurement as well as IR spectra. The crystal is of triclinic system, space group P1, C_（90）H_（52）Eu_2N_4O_（18）, M_r = 1781.32, a = 9.8697（4）, b = 16.7466（6）, c = 22.2556（10） A, α = 87.113（3）, β = 77.575（5）, γ = 89.458（3）°, V = 3587.8（3） A^3, Z = 2, D_c = 1.649 g/cm^3, F（000） = 1780, μ（MoKα） = 1.813 mm^（-1）, Rint = 0.0181, R = 0.0260 and wR = 0.0592 for 14000 observed reflections with I 〉 2σ（I）. X-ray analysis shows that the title compound exhibits a 2D layer structure linked by L ligands with two coordination modes and two distinguished conformations, and further linked into a 3D supramolecular architecture through C-H···O weak interactions between hydrogen of phen phenyl ring and the carboxylate oxygen atom of adjacent sheets. In addition, the luminescence property of 1 was investigated.

Responsive mechanism and coordination mode effect of a bipyridine-based two-photon fluorescent probe for zinc ion

The properties of one-photon absorption(OPA),emission and two-photon absorption(TPA)of a bipyridine-based zinc ion probe are investigated employing the density functional theory in combination with response functions.The responsive mechanism and coordination mode effect are explored.The structural fluctuation is illustrated by molecular dynamics simulation.The calculated OPA and emission wavelengths of the probe are consistent with the experimental data.It is found that the red-shift of OPA wavelength and the enhancement of TPA intensity are induced by the increased intra-molecular charge transfer mechanism upon metal binding.The structural fluctuation could result in the blue-shift of TPA wavelength and the decrease of the TPA cross section.The TPA properties are quite different among the zinc complexes with different coordination modes.The TPA wavelength of the complexes with two ligands is close to that of the probe,which is in agreement with the experimental observation.

Isomerism and coordination mode effects on two-photon absorption of tris(picolyl)amine-based fluorescent probes for zinc ions

One-photon absorption and two-photon absorption（TPA） properties of three tris（picolyl）amine-based zinc ion sensors are investigated by employing the density functional response theory in combination with the polarizable continuum model.The different isomer and coordination geometry of each probe are taken into account. Special emphasis is placed on the effects of isomerism and the coordination mode on the optical properties. The intra-molecular charge transfer（ICT）properties are specified by natural bond orbital charge analysis. It is shown that the isomerism has non-negligible effects on TPA properties of free ligands. It is found that both the TPA wavelength and the cross section are highly dependent on the coordination mode. When the zinc ion connects with the picolyl unit in the middle of a ligand, the zinc complex has a large TPA intensity in a long wavelength range due to the increased ICT mechanism.

Applied Mode Coordinate to Solve Dynamic Responses of Antenna Mechanic System

Based on the Lagrange s equation and the finite element method, this paper establishes the dynamic equation of a radar antenna mechanic system which is a high accuracy system and consists of two flexible bodies. Mode coordinates are used to reduce the orders of equation. Finally, the calculation method and engineering example are given when the rotational velocity of antenna is invariable and the wind velocity is 25?m/s. The error of antenna mechanic system can be estimated using the calculation results.

Pb（Ⅱ） and Mn（Ⅱ） Coordination Compounds Involving 5,5＇-（1,4- Phenylene）bis（1H-tetrazole）： Synthesis, Characterization, and Effect on Thermal Decomposition of Ammonium Perchlorate

Two coordination compounds [Pb4（BDT）3（OH）2（H2O）4].H2O （1） and [Mn（H20）6]·（HBDT）2.2H2O （2） [H2BDT= 5,5＇-（1,4-phenylene）bis（1H-tetrazole）] had been hydrothermally synthesized. 1 and 2 had been characterized by single-crystal X-ray diffraction, IR, elemental and thermal analyses. Structural analysis reveals that 1 exhibits 2D layer structure extended through BDT with two different coordination modes rings in transverse and vertical. 2 consists of [Mn（H2O）6]2＋, free HBDT and water. In addition, 1 and 2 were explored as luminescent materials and additives to promote the thermal decomposition of ammonium perchlorate by differential scanning calorimetry.

Self-Sustaining of Critical Park Microgrids Integrating Mobile Emergency Generators Subjective to Major Outage

In the event of a major power outage,critical park microgrids(PMGs)could be self-sustaining if mobile emergency generators(MEGs)are stationed to share energy.However,the need for privacy protection and the value of flexible power support on minute-time scales have not been given enough attention.To address the problem,this paper proposes a new self-sustaining strategy for critical PMGs integrating MEGs.First,to promote the cooperation between PMG and MEG,a bi-level benefit distribution mechanism is designed,where the participants'multiple roles and contributions are identified,and good behaviors are also awarded.Additionally,to increase the alliance benefits,three loss coordination modes are presented to guide the power exchange at the minute level between the MEG and PMG,considering the volatility of renewable generation and load.On this basis,a multi-time scale power-energy scheduling strategy is formulated via the alternating direction method of multipliers(ADMM)to coordinate the PMG and MEG.Finally,a dimensionality reduction technology is designed to equivalently simplify the optimization problem to facilitate the adaptive-step-based ADMM solution.Simulation studies indicate that the proposed strategy achieves the self-sustaining of PMGs integrating MEGs while increasing the economy by no less than 3.1%.

Hydrothermal Syntheses and Crystal Structures of Two Layered Nickel（ll） Coordination Polymers Based on 1,2,3-Benzenetricarboxylic Acid

The hydrothermal reactions of Ni（Ⅱ）, 1,2,3-benzenetricarboxylic acid （1,2,3-H3btc） and 4,4＇-bipyfidine （4,4＇-bpy）/1,2-bis（4-pyridyl）ethane （bpa） yield two layered nickel（II） coordination polymers, [Ni2（l,2,3-btc）（OAc）- （4,4＇-bpy）2（H20）]o2H2O （1） and [Ni（ip）（bpa）] （2） （ip=isophthalate）, respectively. Both complexes are 2-D coordi- nation network based on 1-D Ni-carboxylate chains. The 1,2,3-btc ligand adopts 3-bridging mode in complex 1, but transformed to isophthalate （ip） ligand through decarboxylation in 2. The formation of the two complexes indicates that hydrothermal conditions and in-situ ligand reaction have significant effect on constructing coordination polymers.

Unusual Coordination Mode of Tetradentate Diiminedioxime Ligand in a Mononickel(Ⅱ) Complex:Synthesis, Characterization, and Computational Study

In this work, it is found that 1,8-dihydroxyimino-1,2,7,8-tetraphenyl-3,6-diazocta-2,6-diene(PhdoenH2) could react with nickel(Ⅱ) salt to yield a mononickel complex Ni(Phdoen)(1) with unusual [2N2O]-coordinated mode, while the analogous diimine-dioxime ligands usually form the [4N]-coordinated mode. The novel complex 1 has been carefully characterized by 1H NMR, elemental analysis, and X-ray diffraction structure analysis. The influences of the coordination modes on the structures and redox properties have been further investigated. Theoretical investigations revealed that the different coordination modes were ascribed to the thermodynamic properties of ligands.

Three-dimensional analysis of relationship between relative orientation and motion modes

Target motion modes have a close relationship with the relative orientation of missile-totarget in three-dimensional highly maneuvering target interception. From the perspective of relationship between the sensor coordinate system and the target body coordinate system, a basic model of sensor is stated and the definition of relative angular velocity between the two coordinate systems is introduced firstly. Then, the three-dimensional analytic expressions of relative angular velocity for different motion modes are derived and simplified by analyzing the influences of target centroid motion, rotation around centroid and relative motion. Finally, the relationships of the relative angular velocity directions and values with motion modes are discussed. Simulation results validate the rationality of the theoretical analysis. It is demonstrated that there are significant differences of the relative orientation in different motion modes which include luxuriant information about motion modes. The conclusions are significant for the research of motion mode identification,maneuver detection, maneuvering target tracking and interception using target signatures.

Asymmetric Synthesis of Anti-tuberculosis-specific Drug TBAJ-876 through Synergistic Li/Li Catalysis

TBAJ-876, developed by TB Alliance, a novel anti-tuberculosis-specific drug, has entered Phase II clinical trials. Herein, the first asymmetric synthesis of TBAJ-876 has been realized using synergistic Li/Li catalysis with excellent yield of 95% and 88 : 12 er (99.6 : 0.4 er, 10 : 1 dr after simple recrystallization). Furthermore, DFT calculations and 7Li-NMR analysis illustrated the mechanism of the synergistic reaction: a chiral Li-complex activates the nucleophile to control the stereoselectivity, while the other achiral Li-complex activates the electrophile to catalyze the carbonyl addition reaction. Additionally, this protocol has been successfully carried out at 5 gram-scale, showing its industrial potential.

Trinuclear Dy(III)Single-Molecule Magnets with Two-Step Relaxation

The reaction of DyCl_(3)·6H_(2)O with a rigid diacylhydrazone ligand(H_(2)L)afforded a trinuclear precursor[Dy_(3)L_(2)Cl_(3)(H_(2)O)_(2)(CH_(3)OH)]Cl_(2)·3CH_(3)OH(1).The replacement of the Cl-ions and the coordinating solvents by the aryloxides ligands(Lx)-yields three trinuclear complexes[Dy_(3)L_(2)(Lx)_(5)]·nsol(x=1,2-naphthol(2);x=2,7-hydroxycoumarin(3);and x=3,phenol(4)).In complexes 2-4,two end Dy^(3+)centers adopt almost identical N_(4)O_(4) coordination sphere of D6h geometry while the central one adopts N_(4)O_(5) coordination sphere in Cs geometry.Magnetic measurements reveal weak antiferromagnetic interactions in the hydrated samples 2e-4e and two-step slow relaxation process under zero dc field with effective energy barriers Ueff of 439 and 91 K,353 and 40 K,466 and 89 K for SR and FR in 2e-4e,respectively.Such dynamic magnetic behaviour for 4 persists in the magnetically diluted sample of 4@Y.Complex 4 possesses the short Dy-O_(aryloxide) bond distance of 2.055(18)Å,and the largest Ueff among the reported linear trinuclear dysprosium complexes.Moreover,the functionalized aryloxides ligands(Lx)-show photoluminescence via intramolecular energy transfer,making 2e-4e luminescent Dy^(3+)SMMs with high energy barriers.

Effect of Alkylaluminum Activators on Ethylene Trimerization Based on 2,5-DMP/Cr（III）/TCE Catalyst System

Ethylene trimerization toward 1-hexene catalytic system with 2,5-dimethylpyrrole （2,5-DMP）/Cr（III）/alkylaluminum/tetrachloroethane （TCE） was investigated. The effects of various cocatalysts on catalytic activity and product selectivity were discussed. The results showed that triethylaluminum （TEA）, trimethylaluminum （TMA）, tri-n-hexylaluminum （TNHA） and tri-isobutylaluminum （TIBA） were all effective cocatalysts for ethylene trimerization toward 1-hexene. 2,5-DMP/Cr（III）/TEA/TCE catalytic system afforded the best results for ethylene trimerization, while reducing the level of by-product formation. Some specific interaction modes of alkylaluminum with active Cr species in the catalytic cycle were proposed to explain the effect of cocatalyst on catalytic activity and 1-hexene selectivity.

Endohedral Metallofullerenes: An Ideal Platform of Sub-Nano Chemistry

What is the most favorite and original chemistry developed in your research group?Creation of no vel metal-carb on hybrid molecules with unconve ntional techniques,known as endohedral metallofullerenes,and the unexplored chemistry hidden inside them,especially discovery of the unprecedented bonding between rare earth metal ions and a variety of novel metal clusters,e.g.,Ti_(3)C_(3) and Dy_(2)N_(4).

Variable Learning-Memory Behavior fromπ-Conjugated Ligand to Ligand-Containing Cobalt(II)Complex

In the information-explosion era,developing novel algorithms and memristive devices has become a promising concept for next-generation capacity enlargement technology.Organic small molecule-based devices displaying superior learning-memory performance have attracted much attention,except for the existence of poor heat-resilience and mediocre conductivity.In this paper,a strategy of transforming an organic-type data-storage material to metal complex is proposed to resolve these intrinsic issues.A pristine NDI-derivative(NIPy)and its corresponding Co(II)complex(CoNIPy)are synthesized for the purpose of electrical property investigation.CoNIPy complex-based memristive device exhibits superior ternary WORM memory performance compared with the binary behavior of NIPy,including>104 s of reading,lower threshold voltage(V_(th)),1:10^(2):10^(5)of OFF/ON1/ON2 current ratio,and long-term stability in heating environment.The variable learning-memory behavior can be attributed to the enhanced ligand-to-metal charge transfer(LMCT)and improved redox activity after the introduction of central metal atom and coordination bond.These studies on material innovation and optimal performance are of great importance not only for environmentally-robust memristive devices but also for practical application of a host of organic electronic devices.

The development of molecular and nano actinide decorporation agents

Internal contamination of actinides has led to significant health hazards to the public and workers in the context of nuclear power plant accidents,uranium ore mining,and reprocessing of the used fuel.An effective sequestering agent that is able to remove accidentally incorporated actinides in vivo with low toxicity is always in urgent need.The molecular decorporation ligands have been the most widely researched agents for the past few decades,while preliminary studies of functionalized nanoparticles have shown their clear advantages in metal binding selectivity,toxicity,and oxidative stress alleviation.Herein,the state-of-the-art of those two types of decorporation agents is presented with special attention being paid on the correlation between the solution and solid-state chemistry of those agents with actinides and the corresponding decorporation efficacies.

Crystal Structure and Photoluminescence Properties of Two Barium（II） MOFs

In this article, two Ba（II） metal-organic frameworks（MOFs）, {[Ba（BPS）（H2O）2]＇H2O}n（1） and [Ba（BPS）（H2O）R]n（2）（H2BPS=4,4＇-bibenzoic acid-2,2＇-sulfone）, were synthesized and characterized. X-Ray crystal structural analyses reveal that compounds 1 and 2 have different structures, which is probably related to different coordination modes of ligand in compounds 1 and 2. It is remarkable that compounds 1 and 2 both show excellent thermal stability. The solid-state emission spectra reveal that compounds 1 and 2 both present strong luminescence emission bands at room temperature.

A theoretical study on the alkene insertion step in Rh-Yanphos catalyzed hydroformylation

This paper studied the mechanism of the alkene insertion elementary step in the asymmetric hydroformylation （AHF） catalyzed by RhH（CO）2[（R,S）-Yanphos] using four alkene substrates （CH2=CH- Ph, CH2=CH-Ph-（p）-Me, CH2=CH-C（==O）OCH3 and CH2=CH-OC（=O）-Ph, abbreviated as A1-A4）. Interestingly, the equatorial vertical coordination mode （A mode） with respect to the Rh center was found for AI and A2 but not for A3 and A4, although the equatorial in-plane coordination mode （E mode） was found for A1 -A4. The relative energy of the E mode of the -q2-intermediates is lower than that of the A mode. In the alkene insertion step, Path 1 is more favorable than Path 2 for this system. As for AI and A2, there could be a transformation between 2eq and 2ax.

Preparation of Polymer-Functionalized Iron Oxide Nanoparti-cles and Their Biomedical Properties

Superparamagnetic iron oxide nanoparticles with narrow size distributions were successfully prepared in large scale by a facile one-pot synthetic method in the presence of hydrophilic polymers, such as polyethylene glycol dia-cid （HOOC-PEG-COOH） and poly（acrylic acid） （PAA）. The as-prepared products were investigated in detail by powder X-ray diffraction （XRD）, thermogravimetric analyses （TGA）, transmission electron microscopy （TEM）, high-resolution transmission electron microscopy （HRTEM）, dynamic light scattering （DLS）, and vibrating sample magnetometer （VSM）. The interaction between polymers and iron oxide nanoparticles was investigated using Fou-rier transform infrared spectrometry （FT-IR）. The results show that polymers can be attached onto the surface of iron oxide nanoparticle by bridging coordination and monodentate fashion, respectively. The interaction affects iron oxide nanoparticle properties significantly, such as XRD diffraction intensity, hydrodynamic diameter, isoelectric point, and saturation magnetization. Furthermore, the results of in vitro experiments indicated that iron oxide-PEG-COOH nanoparticle is more cytotoxie than iron oxide-PAA nanoparticle due to different coordinating modes.