Synthesis,Structure,and Properties of{[Mn(ADA)(Phen)]·(H2O)2}n Constructed from Azobenzene-4,4'-dicarboxylic Acid and 1,10-Phenanthroline

One coordination polymer（CP） {[Mn（ADA）（Phen）]（H2O）2}n（1, H2ADA = azobenzene-4,4＇-dicarboxylic acid, Phen = 1,10-phenanthroline）, has been synthesized via hydrothermal reactions. CP 1 was characterized by elemental analyses, IR spectra, thermal behaviors, and X-ray single-crystal diffraction. In CP 1, each ADA（2-） ligand bridges two Mn（2＋） to give one-dimensional zigzag chains with the Mn···Mn separations of 17.6911 and 16.3976 A, which generates a three-dimensional supramolecular structure by means of strong π···π interaction and hydrogen bonding. It crystallizes in triclinic, space group P1, with a = 7.6200（13）, b = 9.1530（15）, c = 18.262（2） A, α = 88.467（3）o, β = 84.145（2）o, γ = 77.542（2）o, V = 1237.2（3） A3, Z = 2, C（26）H（20）MnN4O6, Mr = 539.40, Dc = 1.448 g/cm3, F（000） = 554, S = 1.018, R = 0.0531 and w R = 0.1094. In addition, natural bond orbital analysis was performed by the B3 LYP/LANL2 DZ method of Gaussian 09 Program. The fluorescence, magnetic, and electrochemical properties of 1 have been investigated.

Two New Silver Coordination Polymers Constructed from 3,3-Azodibenzoic Acid and Different Pyridine Derivatives:Syntheses,Structures and Fluorescent Properties

Two coordination polymers（CPs）,{[Ag（ADA）（0.5）（DPE）]·H2O}n（1） and {[Ag（ADA）（0.5）（Bipy）（0.5）]·H2O}n（2）,（H2ADA = 3,3-azodibenzoic acid,DPE = 1,2-di（4-pyridyl）-ethylene,Bipy = 4,4？-bipyridine）,have been synthesized via solvothermal reactions of Ag＋ with ADA^2- and/or DPE,Bipy.CPs 1 and 2 were characterized by elemental analyses,IR spectra,thermal behaviors,and X-ray single-crystal diffraction.CPs 1 and 2 feature ＂Ag···Ag＂ subunits.CP 1 shows a 3D construction,in which the ＂Ag···Ag＂ subunits extend through ADA^2- and DPE ligands using μ6-kO,O;kO;kO;kO,O;kO;kO and μ2-kO;kO coordination modes,respectively.It crystallizes in triclinic system,space group P1,with a = 0.3808（18）,b = 1.2476（6）,c = 1.309（6） nm,α = 76.757（5）,β = 84.649（5）,γ = 86.809（5）o,V = 0.6024（5） nm^3,Z = 2,Mr = 351.11,C（13）H（11）AgN2O3,Dc = 1.936 g/cm3,F（000） = 348,S = 1.064,R = 0.0323 and w R = 0.0689.CP 2 exhibits a 3 D supramolecular structure,in which the ＂Ag···Ag＂ subunits are connected by ADA^2- and DPE ligands with μ6-kO;kO;kO,O;kO;kO and μ2-kO;kO coordination modes,respectively.Ultimately,through hydrogen bond and π···π interaction,the ＂Ag···Ag＂ subunits stabilize the 3D supramolecular structure of 2.It crystallizes in monoclinic,space group C2/c,with a = 25.301（15）,b = 13.197（8）,c = 6.970（4） nm,β = 102.597（7）o,V = 2.271（2） nm^3,Z = 8,C（12）H（10）AgN2O（2.50）,Mr = 330.09,Dc = 1.931 g/cm^3,F（000） = 1304,S = 1.082,R = 0.1107 and wR = 0.2984.The fluorescence properties of CPs 1 and 2 have been also investigated.

Mn(Ⅱ) Based Coordination Polymer Involving 1,2,4,5-Benzenetetraboxylic Acid and 4,4-Bis(imidazol-1-ylmethyl)biphenyl: Synthetic, Structure and Magnetic Property

A novel Mn（Ⅱ）coordination polymer（CP）,[Mn（BBA）0.5（BIYB）]n（1）,was gained by the 1,2,4,5-benzenetetracarboxylic acid（H4BBA）,4,4-bis（imidazol-1-ylmethyl）biphenyl（BIYB）,and Mn（CH3COO）2·4H2O under hydrothermal reaction.CP 1 was characterized and structurally determined by elemental analyses,PXRD,IR spectra,thermal behaviors,and X-ray single-crystal diffraction.The framework structure of 1 shows a novel（2,5,6）-connected 3Dnetwork with a Schlafli symbol of（43.66.8）2（46.69）（6）2.It crystallizes in triclinic system,space group ■,with a=7.5898（5）,b=9.8201（6）,c=14.1307（9）?,α=97.5850（10）,β=99.6810（10）,γ=111.6580（10）o,V=943.01（10）?3,Z=2,C23H15MnN 4O4,Mr=466.33,Dc=1.462 g/cm3,F（000）=476,S=1.082,R=0.0361 and wR=0.1008.The magnetic property of CP 1 was investigated.The weak antiferromagnetic interactions are observed between the Mn（Ⅱ）ions.

Boron Group Ions Direct Conversion of Carbon and Methane into Ethylene in DFT Study

In this study, density functional theory calculations reveal how boron group ions M^+(M = B, Al, Ga, In, and Tl) directly convert carbon and methane into ethylene at room temperature. M^+ reacts with the carbon atom to form the cation MC^+. Then, the reaction of MC^+ with methane leads to the cleavage of metal-carbon bond and the formation of CH2CH2 through C-C coupling, with the ion M^+ serving as a leaving group. The cycle then begins again. The mechanism of C/CH4 system catalyzed by five ion types is investigated herein, and the reasons for the different reactivity of five ion types are determined. The moderate strength of the Al^+-C bond results in Al^+ being the only appropriate catalyst of M^+(M?=?B, Al, Ga, In, and Tl) that can catalyze methane and carbon into ethylene.

DFT Study on the Germanium Ion Activated C–H Bond in Methane

Thermal reactions of methane with the main group metal cations Ge＋,GeO＋,GeOH＋ and OGeOH＋ were investigated by state-of-the-art quantum chemical calculations.For GeO＋/CH_4,a H atom in CH_4 abstracted by the O atom in GeO＋ to form GeOH＋ and CH_3˙constitutes the channel mainly.The barrier-free process,combined with a large exothermicity,suggested a fast and efficient reaction in agreement with the experiment.For OGeOH＋ and CH_4,the intermediates and products of the most favorable path were below the reactant asymptote,and the reaction was easy to take place,while for Ge＋ and GeOH＋,the activation of C-H bond in methane was hard to happen under ambient temperature.The results showed,in contrast to the inertness of Ge~＋ and Ge OH＋,the GeO＋ and OGeOH＋ can activate the H_3C-H bond.The NBO natural charge and molecular electrostatic potential were used to analyze the four main group metal germanium constructions.The phenomenon suggested that ligands affect the electronic character and tune the chemical features of metal germanium center.