Ultra-microporous Metal-organic Framework with High Concentration of Free Carboxyl Groups and Lewis Basic Sites for CO_2 Capture at Ambient Conditions

How to rationally design effective and practical CO_2 adsorbent is a great challenge. Herein, an ultra-microporous metal-organic framework(FJI-H19) with high concentration of free carboxyl groups and uncoordinated Lewis basic sites has been synthesized from a multi-dental ligand with a high proportion of polar CO_2-philic atoms. FJI-H19 displays a relatively high CO_2 volumetric uptake(120 cm^3?cm^(–3)) with high selectivity under practical atmosphere(298 K and 1 bar). Further researches demonstrate that such high adsorption results from an unusual synergistic effect from free carboxyl group and uncoordinated N atoms. This result will provide a potential strategy for developing more effective and pratical CO_2 adsorbent based on MOFs.

Synthesis and Crystal Structure of a Macrocycle[Cu(dadm)(mal)(H_(2)O)]_(2)·2H_(2)O

The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, space group P21/c with a = 15.231(3), b = 11.847(2), c = 9.801(2) ? b = 106.75(3)o, V = 1693.5(6) 3, Z = 2, C32H40Cu2N4O12, Mr = 799.76, Dc = 1.568 g/cm3, ?(MoKa) = 0.71073 ? = 1.325 mm-1, F(000) = 828, the final R = 0.0531 and wR = 0.1244 for 3421 observed reflections with I > 2s(I). Each Cu(II) is coordinated by two oxygen atoms from a mal ligand, two nitrogen atoms from two dadm ligands and a water oxygen atom to form a triangle bipyramidal motif. The title compound possesses a distorted macrocycle enclosed by dadm with approximate dimensions of 8.3 ??5.9 ?

Syntheses and Crystal Structures of Two 3D Zinc(II) Compounds Involving Coordination and Hydrogen Bonds

Two zinc（Ⅱ） compounds, [Zn（L）（H2O）2]n 1 and [Zn（4,4＇-bpy）（H2O）4]（L） 2 （H2L = trans,trans-1,3 butadiene 1,4-dicarboxylic acid）, were synthesized by hydrothermal methods and characterized by single-crystal X-ray diffraction analyses. Compound 1 crystallizes in monoclinic, space group C2/c with a=15.4970（16）, b = 5.4976（6）, c = 10.7113（12） A, β=96.298（6）°, C6H8O6Zn, Mr = 241.50, V = 907.06（17） A^3, Z = 4, D, = 1.768 g/cm^3, F（000） = 488,μ = 2.703 mm^-1, S = 1.060, the final R = 0.0256 and wR = 0.0660 for 968 observed reflections with Ⅰ 〉 2σ（Ⅰ）. Compound 2 crystallizes in triclinic, space group P1^- with a = 6.915（2）, b = 7.166（2）, c = 10.363（3） A, α = 73.250（4）, β = 84.429（4）, γ = 61.605（3）°, C16H2ON2O8Zn, Mr = 433.70, V = 432.1 （2） A^3, Z = 1, D, = 1.667 g/cm^3, F（000） = 224 and μ= 1.471 mm^-1, S = 1.118, the final R = 0.0486 and wR = 0.1077 for 1352 observed reflections with Ⅰ〉 2σ（Ⅰ）. Upon using the assembly strategy of combination of coordination polymer chains with intermolecular hydrogen bonds, three-dimensional frameworks of complexes 1 and 2 were formed.

Syntheses and Crystal Structures of Two Isomeric Au Complexes

Two new isomeric Au complexes, Au（PPh3）（bmt）, have been synthesized via the reaction of Au（PPh3）CI with 2-benzimidazolethiol （Hbmt） in dichloromethane （CH2Cl2） solution. Their crystal structures were determined by elemental analysis and single-crystal X-ray diffraction studies. Complex 1 crystallizes in the monoclinic system, space group C2/c with a = 19.589（2）, b = 21.1368（15）, c = 23.424（2） A, β = 108.346（4）°, V= 9206.1（14） A3, Mr = 1216.85, Dc = 1.756 g/cm3, μ = 6.566 mm^-1, F（000） = 4704, Z = 8, the final R = 0.0563 and wR = 0.1028 for 8125 reflections with I 〉 2σ（I）. Complex 2 crystallizes in the monoclinic system, space group P21/n with a = 9.627（3）, b = 21.384（8）, c = 22.308（8） A, β = 92.068（6）°, V= 4590（3） A3, Mr = 1216.85, Dc = 1.761 g/cms, μ = 6.585 mm^-1, F（000） = 2352, Z = 4, the final R = 0.0500 and wR = 0.0883 for 10477 reflections with I 〉 2σ（i）. X-ray diffraction studies reveal that complexes 1 and 2 both feature a 1D chain along the a axis.

Synthesis and Crystal Structure of a 3-D Hydrogen-bonded Supramolecular Decavanadate Compound [Habo]_6[V_(10)O_(28)]·2C_3H_7OH·2H_2O

A new inorganic-organic hybrid supramolecular compound [Habo]6[V10O28]·2C3H7OH·2H2O 1 （abo = R（-）-2-amino-1-butanol） has been synthesized from VO2^＋ in organic solvents and its crystal structure was reported as follows： monoclinic, space group P21/n, a = 11.419（9）, b = 16.811（16）, c = 15.521（12） A, β= 102.98（2）°, V= 2903（4） A^3, Z = 4, C15H46N3O19V5, Mr = 827.25, Dc = 1.893 g/cm^3, 2（MoKα） = 0.71073 A, μ = 1.636 mm^-1, F（000） = 1696, the final R = 0.0696 and wR = 0.1361 for 4641 observed reflections with I 〉 2σ（I）. The compound is based on decavanadate clusters [V10O28]^6-. The hydrogen bonding interactions among Habo^＋ cations, solvents and decavanadate clusters extend 1 into a three-dimensional supramolecular architecture.

Syntheses，Structures and Spectroscopic Properties of Mo（W）－Cu－S－Cluster Compounds with Dialkyldithiocarbamate Ligands

This paper presents the synthetic and structure studies of molybdenum（tungsten）-copper-sulphur-dialkyldithiocarbamate cluster compounds.The reactions of（M=Mo,W;n=0,2）,CuCl,and R2dtc￣-（R2=Me2,Et2,C4H8,C5H10） yield a series of tetra-,hexa-,and heptanuclear cluster compounds.Their spectroscopic properties and the synthetic reaction mechanism are discussed.

Nickel Group Complexes With Thiolate or/and Phosphine Ligands.Synthesis and X-ray CrystalStructure of 〔Ni_2(pdt)_2 (PEt_3)_2〕

The reactions of nickel group M2+ with thiolate and phosphine inMeOH yield mononuclear and binuclear complexes. Ni2 (PEt3 ), (pdt )2 (pdt = 1, 2propanedithiolate) was synthesized and analyzed by single crystal X--ray diffractionmethod. The complex is monoclinic with space group P21 /c, Mr= 566. 16 a = 18. 737(5), b=9. 906(4), c= 14. 540(10) A; V=2697. 65 A3, Dc = 1. 394 g/cm3 for Z=4; the final R(Rw) = 0. 062(0. 072). The complex is a dimer, where the Ni atoms arelinked by two sulphur atoms from SC3H6S2- (pdt2- ) ligands and each Ni atom is fourcoordinated by one P and three S atoms with distorted square--planar geometry. The Ni--Ni distance is 3. 025 .A, the average Ni--S, Ni--P distances are 2. 187 and 2. 194A, respectively.

Investigation on Magnetic Properties of Exchange Coupled Transition Metal Complexes Ⅱ．Theoretical Model for Trinuclear Complexes

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面向战略性新兴产业的科技成果转化机制探索

战略性新兴产业是未来的支柱性产业,具有发展潜力高、经济带动性强、技术知识密集等特点。三螺旋模型是研究科技成果转移转化问题中最常用的模型之一,但应用传统三螺旋模型指导战略性新兴产业的科技成果转移转化存在局限性。本文以中国科学院海西研究院在战略性新兴产业科技成果转移转化方面的探索与实践为例,分析了三螺旋模型在实际应用中的表现模式,提出适用于战略性新兴产业科技成果转移转化的新型三螺旋模型,并提出未来应用的改进建议。

Ultrasmall Lanthanide-doped NaMgF Nanocrystals: Controlled Synthesis and Optical Properties

Orthorhombic-phase NaMgF3, composed of bio-friendly elements of Na, Mg and F, is considered to be an ideal host matrix for preparing trivalent lanthanide(Ln3+)-doped luminescent nanocrystals(NCs) with color-tunable emissions for diverse biological applications. However, the preparation and the survey on optical properties of ultrasmall(< 10 nm) Ln3+-doped NaMgF3 NCs remain nearly untouched to date. In this paper, we report a series of monodisperse Ln3+-doped orthorhombic-phase NaMgF3 NCs with an average size of ~10 nm that was synthesised by using a modified high-temperature co-precipitation method. Utilizing Eu3+ ion as an efficient optical/structural probe, the successful hetero-valence doping of Ln3+ ion into the lattice of NaMgF3 NCs is well-established irrespective of their different valences and radii between the host cation(e.g. Mg2+) and Ln3+ dopant. Benefiting from this, desirable upconversion luminescence(UCL) ranging from ultraviolet(UV) to visible and to near-infrared(NIR) spectral regions can be easily obtained after the doping of typical UCL couples of Yb3+/Er3+, Yb3+/Tm3+ and Yb3+/Ho3+ into the NaMgF3 NCs upon excitation by using a 980-nm diode laser.

Atom Response Theory of Nonlinear Optical Responses and Its Applications

Second-order nonlinear optical(NLO)crystalline materials are fundamentally and technologically important for their ability to double or triple the frequency of lasers.This article provides a brief review of the atom response theory(ART)of NLO responses recently developed on the basis of the partial response functional method.The ART analysis enables one to quantitatively evaluate the contributions of individual constituent atoms to the second harmonic generation(SHG)response of a NLO crystal material on the basis of first principles DFT calculations.The general partitioning principles developed in our recent work provide the conceptual foundation for determining the functional motifs of SHG responses.In this mini review we will focus on the concepts and principles as well as on applications with examples.Some practically important empirical rules resulting from the ART studies will also be reviewed.

Synthetic and structural chemistry of hexacobalt cluster compounds——Ⅱ. Preparation and structure of Co_6(μ_3-S)_8(Ph_2PCH_2P(O)Ph_2)_6

Co_6(μ_3-S)_8(Ph_2PCH_2P(O)Ph_2)_6, MW=3012.5, space group R, has the hexagonal parameters, a=26.764(10), c=16.979 (10), V=10532.8~3, Z=3. Mo Kα radiation, λ= 0.71069, Dc=1.425 g/cm^3, μ=9.94 cm^(-3), F(000)=4650, R=0.073 and Rw=0.077 for 1965 observed unique reflections with I>3σ(I). The molecular structure consists of a distorted octahed- ral Co_6-core. The Co-Co and Co-S distances fall in the range of 2.805-2.838 and 2.213-2.253, respectively.

A cobalt-selenium cluster with triethylphosphine: preparation and structure of Co_6(μ_3-Se)_8(PEt_3)_6·THF

Co_6 (μ_3-Se)_8 (PEt_3)_6·THF, MW=1766.4, space group R, has the trigonal parameters, a=11.890(2)°, α=92.72(2)°, V=1670.4~3, Z=1. Mo Kα radiation, λ=0.71073, Dc=1.749 g/cm^3, μ= 59.18 cm^(-3), F(000)=870, R=0.058 and Rw=0.067 for 1529 observed unique reflections with I>3σ(I). The molecular structure consists of an idealized octahedral Co_6-core. The Co-Co distances fall in the range of 2.909-2.9122.