{[(n-C_4H_9)_4N]_2Ag_(4.95)Cu(Ⅰ)_(1.05)I_8}_n聚合物的合成和晶体结构

标题化合物由AgI、CuI和(n-C4H9)4NI在DMF溶剂中直接反应而得。晶体结.构通过单晶X-射线衍射法确定,其晶体属于单斜晶系,空间群P21/c,a=9.4342(4),b=15.7638(7),c=18.877(1)??=100.65(1)?V=2758.9(2)3,化学式C32H72N2Ag4.95Cu1.05I8,Mr=2100.79,Dc=2.529g/cm3,Z=2,(MoK?=6.618cm-1,F(000)=1930。在1.70≤?≤27.46范围内收集到22473个衍射点,独立衍射点6175(Rint=0.0753),其中可观测衍射点4158个(I>2(I))。晶体结构用直接法和差傅立叶合成方法找出初步结构模型,再分别对Ag和Cu的坐标进行修正,最后用全矩阵最小二乘法对266个变量进行精修,最终偏离因子R=0.0476,wR=0.1315。标题化合物的结构由[(M6I8)-]阴离子链和链间的n-Bu4N+阳离子组成。     

Synthesis and Crystal Structure of a Novel One-dimensional Coordination Polymer [ （C14H18N2）（Pb2i6）]n

1 INTRODUCTION The organic-inorganic hybrid material is a new type of composite between organic and inorganic polymers, and has captured the imaginations of che- mists due to its potential applications in electric con- ductivity, magnetism, ion exchange…     

Syntheses, Crystal Structures and Characterization of Layered and Layer-pillared Zinc Arsonates

Two zinc arsonate coordination polymers, Zn(4-apa)·H2O (1, 4-apaH2 = 4-amino- phenylarsonatic acid) and Zn(4-apa) (2), have been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal and powder X-ray diffraction. Crystal data for 1: monoclinic, space group C2/c with a = 23.056(5), b = 5.4224(11), c = 15.027(3) , β = 121.22(3)°, V = 1606.6(6) ?3, Dc = 2.468 g·cm-3, F(000) = 1168, μ = 7.122 mm-1, Z = 8, the final R = 0.0309 and wR = 0.0752 for 1763 observed reflections with I > 2σ(I). For 2: monoclinic, space group P21/c with a = 8.7852(18), b = 9.2744(19), c = 9.752(2) , β = 103.45(3)°, V = 772.7(3)3, Dc = 2.410 g·cm-3, F(000) = 544, μ = 7.387 mm-1, Z = 4, the final R = 0.0321 and wR = 0.0741 for 1696 observed reflections with I > 2σ(I). The structure of 1 shows a two-dimensional (4,4)-network composed of an inorganic ladder chain bridged by the phenyl-linkers of 4-apa ligands. Compound 2 exhibits a 3D layer-pillared framework with crb net, in which inorganic (4-82)-networks are joined by the phenyl-linkers.     

Crystallographic Characterization of the Novel Inorganic-organic Hybrid Coordinated Polymer:[(C22H50N2)(Ag2I4)]n

1 INTRODUCTION Halometallates are the particularly suitable systems for designing the construction of unusual low-dimensional structural archetypes, from which peculiar electronic, thermal, catalytic and magnetic properties can arise. The syntheses of th…     

Syntheses, Structures, and Some Properties of Three Vanadium Selenites

Three novel vanadium selenites with the formulae [（VO2）（1,10-phenanthtoline）（SeO3H）]2 1, [（VO2）（2,2′-bipyridine）]2（SeO3） 2 and [（VO）（H2O）（SeO3）2]2（HaEDD） 3 （EDD = N1,N1′-（ethane-1,2-diyl）diethane-1,2-diamine） were hydrothermally synthesized, and characterized with elemental analysis, FT-IR spectrum, Raman spectrum, TG-DTA analysis, EPR spectra, and single-crystal X-ray diffraction analysis. Compound I belongs to the triclinic system, space group P1^- with a = 7.7527（5）, b = 9.5345（10）, c = 9.8192（8） A^°, α = 92.712（3）, β = 105.540（3）, γ = 108.154（4）°, V = 657.66（1） A^°^3, Mr = 782.22, Z = 1, F（000） = 384,μ（MoKa） = 3.544 mm^-1, R = 0.0432 and wR = 0.1142; Compound 2 is of orthorhombic system, space group F212121 with a = 7.6574（15）, b = 14.916（3）, c = 19.085（4） A, V = 2179.8（8） Aa, Mr = 605.21, Z = 4, F（000） = 1200, μ（MoKa） = 2.579 mm^-1, R = 0.0338 and wR = 0.0658; Compound 3 belongs to the triclinic system, space group P1^- with a = 9.247（2）, b = 9.659（2）, c = 7.2651（19） A^°, α = 98.171（7）, β = 103.709（5）, γ = 114.712（13）°, V = 550.9（2） A^°^3, Mr = 828.03, Z = 1, F（000） = 400, μ（MoKa） = 7.537 mm^-1, R = 0.0641 and wR = 0.2118. Compound 1 is constructed from alternating corner-shared [VO4N2] octahedra and SeO3H units, forming a dimeric vanadium unit. These assemblies are further linked into an infinite chain via hydrogen bonds along the a axis. In the structure of 2, two distinct V centers form centrosymmetric [V2O6N4] clusters through edge-sharing, and the SeO3 unit serves as a capping unit to fix the oxovanadate cluster. In the structure of 3, each [VO6] octahedron shares four oxygen atoms with adjacent Se atoms, while every SeO3 unit shares two oxygen atoms with neighboring V atoms. This connectivity of alternating VO6 and SeO3 units results in a joint-like chain. Based on the TGA analysis, these three compounds are thermally stable under 200℃ .     

Addition Reactivity of C_（36） Cage Controlled by the Curvature and the Electronic Factors：A DFT Study

The molecular geometries and electronic structures of the fullerene derivatives C36(OH)n(n = 1～2) have been investigated on the basis of density functional theory calculation at the B3LYP/6-31++G* level.The geometry optimization results indicate that the location of C2 atom is the most active site in the three potential adding patterns,and the C1 or C2 site has a larger binding energy than C3 for the addition reactions of C36(D6h) cage and OH radicals resulting from the larger curvature.The electronic structure calculation results disclose that the C2 site has larger electronic population in HOMO and larger spin density,and the addition reaction on the C2 site need overcome a lesser energy gap than that on the C1 or C3 site.Thus,the addition is controlled jointly by the curvature and the electronic factors.Besides,when two hydroxyls are added to the C36 surface,the C2 sites are also the most active locations.The most stable addition adduct of C36(OH)2 is the isomer which holds Ci symmetry,and the spin multiplicity seriously affects the stabilities of the adducts.     

Synthesis and Crystal Structure of Compound[Ni（bipy）3][（μ—oxo）Fe2Cl6]

1 INTRODUCTION Recently, functional models for oxo-bridged diiron (Ⅲ) complexes have received much attention[1, 2]. They provide structural models for diiron sites in several proteins involved in oxygen storage of hemerythrin[3] and oxygen activation of methane monooxygenase[4]. In addition, several synthetic FeOFe (-oxo) diiron(Ⅲ) complexes show catalase-like activity[5, 6]. One of our studies in this respect is trying to synthesis -oxo bridged diiron complexes. The compound [Fe(ph…     

Study of Two Puzzled Questions on the Fullerene C_（70）：A First-principles Study

The cycloaddition reactions of NH to different bonds on C70 have been studied by the first-principles calculations.The results indicate that the reactivity of cycloaddition reactions is determined by the directional curvature,KD,and the larger binding energy of Eb on the bond C5-C'5 can be ascribed to the unique bond which can be treated as the shortest bond of(5.5)-SWCNT in the four [6,6] ring fusion bonds.This work also discloses that the energy gap of different spin states is decided by the electronic density,and that of the frontier obitals for the bond C5-C'5 is larger than the value for the C4-C'4 bond.Furthermore,the transition state investigation of the two bond addition reactions provides a reaction barrier of 11.10 kcal/mol for the NH cycloaddition to the C5-C'5 bond;whereas,the addition reaction on C4-C'4 is a spontaneous pathway.Herein,the dynamics effect illustrates the [2+1] cycloaddition reaction on the equatorial C5-C'5 bond to be unfavorable.     

Synthesis and Crystallographic Characterization of Complex [(CH3)3NCH2CH2N(CH3)3][HgI4]·H2O Containing Novel Cation

The title compound has been synthesized by the reaction of HgI2 and [(CH3)3- NCH2CH2N(CH3)3]I2 with pH = 7.5 at room temperature, and its crystal structure was determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in monoclinic system, space group P21/c with a = 8.3075(8), b =15.8084(19), c =15.390(2)(°A), β = 95.192(4)o, V = 2012.9(4)(°A)3, Z = 2, Dc = 2.824 g/cm3, F(000) = 1502, C14H39N4O2Hg2I8, Mr = 1711.87, μ(MoKα) = 13.768 mm-1, the final R = 0.0465 and wR = 0.1293 for 3046 observed reflections with I > 2(I). The title compound consists of cations ([C8H22N2]2+) and anion (HgI42-), which are combined by static attracting forces to form the so-called organic-inorganic hybrid material.     

过渡金属配合物与铀酰-有机框架复合:两例新型铀/铜异金属配合物的合成、晶体结构及其性能研究

在水热条件下,将铜金属配合物插入到铀酰有机框架化合物中,合成了两例新型铀/铜异金属杂化配合物[Cu(bipy)(UO2)(bdc)2·H2 O]n(1),{[Cu(phen)(UO2)(bdc)(bc)(H2O)]·H2O}n(2)(bipy=2,2′-联吡啶,bdc=对苯二甲酸,phen=1,10-邻菲罗琳,bc=苯...