Vapochromic behavior of {Ag2(Et2O)2[Au(C6F5)2]2}n with volatile organic compounds

The vapochromic behaviors of {Ag2L2[Au(C6F5)2]2}n (L = Et2O (1), Me2CO (2), THF (3), CH3CN (4)) were studied. {Ag2L2[Au(C6F5)2]2}n (L = Et2O (1)) was synthesized by the reaction of [Bu4N][Au(C6F5)2] with AgOClO3 in 1:1 molar ratio in CH2Cl2/Et2O (1:2). 1 was used as starting material with THF to form {Ag2L2[Au(C6F5)2]2}n (L = THF (3)). 3 crystallizes in the monoclinic space group C2/c and consists of tetranuclear units linked together via aurophilic contacts resulting in the formation of a 1D polymer that runs parallel to the crystallographic z axis. The gold(I) atoms are linearly coordinated to two pentafluorophenyl groups and display additional Au...Ag close contacts within the tetranuclear units with distances of 2.7582(3) and 2.7709(3) A. Each silver(I) center is bonded to the two oxygen atoms of the THF molecules with a Ag-O bond distance of 2.307(3) A. TGA analysis showed that 1 loses two molecules of the coordinated solvent per molecular unit (1st one: 75-100 degrees, second one: 150-175 degrees C), whereas 2, 3, and 4 lose both volatile organic compounds (VOCs) and fluorinated ligands in a less well defined manner. Each complex loses both the fluorinated ligands and the VOCs by a temperature of about 325 degrees C to give a 1:1 gold/silver product. X-ray powder diffraction studies confirm that the reaction of vapors of VOCs with 1 in the solid state produce complete substitution of the ether molecules by the new VOC. The VOCs are replaced in the order CH3CN > Me2CO > THF > Et2O, with the ether being the easiest to replace. {Ag2(Et2O)2[Au(C6F5)2]2}n and {Ag2(THF)2[Au(C6F5)2]2} n both luminesce at room temperature and at 77 K in the solid state. Emission maxima are independent of the excitation wavelength used below about 500 nm. Emission maxima are obtained at 585 nm (ether) and 544 nm (THF) at room temperature and at 605 nm (ether) and 567 nm (THF) at 77 K.     

CRYSTAL STRUCTURE OF {Ni[(C_4H_9O)_2PS_2](C_(12)H_8N_2)_2} -[(C_4H_9O)_2PS_2]

<正> {Ni C(C4H9O)2PS2] (C12H8N2)2} [C(C4H9O)2PS2], Mr= 795. 60, Monocinic,P2,/n,a=16. 806(2), b=12. 720(2), c=21. 248(2) A. β=98. 454(7)°, V = 4493A3,Z=4,Dc= 1. 18g·cm-3,Mo Ka radiation,A=0. 71069A ,F(000) = 1664, R=0. 102 for 4154 reflections with I≥3σ(I).The crystal structure consists of complex cation {NiC(C4H9O)2PS2](C12H8N2)2}+ and complex anion C(C4H9O)2PS2]-. In the cation, nickel (Ⅱ) atom is coordinated by four nitrogen atoms and two sulfur atoms to form a distorted octahedron.     

{Cu[H_2NC(CH_2OH)_3]_2}{Pic}_2·H_2O的合成与晶体结构

三羟甲基氨基甲烷与苦味酸(Pic)铜在乙醇水混合液中反应,制得少见的不对称氢键连接的超分子化合物{Cu[H2NC(CH2OH)3]2}{Pic}2?H2O。晶体属三斜晶系,空间群为P ,晶胞参数为a = 6.894(1),b = 8.219(1),c = 13.543(3) ? ?= 79.290(1),?= 8 3.36(2), ?= 84.590(1)埃轿狢20H30CuN8O22,V = 746.9(2) 3,Z = 1,Dc = 1.774 g/cm3,F(000) = 411,?= 0.844 mm-1,R = 0.0334,Rw = 0.0863。在配合物的结构单元中, Cu2+位于对称中心,分别与2个四齿配体(三羟甲基氨基甲烷)中的2个OH,1个NH2,三齿配位,呈笼状螯合。而另一个OH,因配体和中心离子构型的限制,不参与配位。     

Synthesis and Crystal Structure of［（n－Bu）_4N］_2［Mo_4O_（10）（OC_（10）H_6O）_2（OCH_3）_2］

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ［（ｎ－Ｂｕ）_４Ｎ］_２［Ｍｏ_４Ｏ_（１０）（ＯＣ_（１０）Ｈ_６Ｏ）_２（ＯＣＨ_３）_２］￥ＬｕＸｉａｏ－Ｍｉｎｇ；ＺｈｕＨｕｉ－Ｊｕ；ＹａｎｇＮｉｎｇ；ＬｉｕＳｈｕｎ－Ｃｈｅｎｇ；ＪｉｎＸ?..     

Crystal Structure of Bis｛1-(2-methoxyethyl)indenyl｝dysprosium Chloride

1　INTRODUCTION　　Organolanthanidecomplexeshavebeenextensivelystudied.However,thestud-iesofindenylrareearthcomplexeswererelativelylimited[1].Althoughaseriesoftri-indenyltetrahydrofuranatolanthanide((C9H7)3Ln·THF)havebeensynthesizedandstudiedbyTsutsuiandGyslingabout30yearsago[2],onlyafewcrystalstruc-turesofindenyllanthanidecomplexeshavebeenreported[1].Moreover,mostofthereportedindenyllanthanidecomplexesweresynthesisedbymetatheticalreactionsofanhydrouslanthanidetrichlorideswithindenyls…     

芳氧功能化咪唑基五氯化铕[HO-4,6-di-tBu-C6H2-2-CH2{CH（NCHCHNiPr）}]2+[EuCl5（THF）]2-的合成与结构

芳氧功能化咪唑盐L+Cl-(L=HO-4,6-di-tBu-C6H2-2-CH2{CH[iPrNCHCHN]})与无水EuCl3分别按照摩尔比为1∶2和1∶3反应成功合成相同芳氧功能化咪唑基五氯化铕L+2[EuCl5(THF)]2-,产物通过元素分析、IR、X-ray射线衍射表征。晶体结构数据表明此配合物属于单斜晶体,空间群P21/c,晶胞参数a=0.96664(8)nm,b=1.63312(12)nm,c=3.6850(3)nm,β=97.600(2)°,V=5.7662(8)nm3,Mr=1060.30,Z=4,Dc=1.221 Mg/m3,μ(MoKα)=1.36 mm-1,F(000)=2200。目标化合物是由阴离子[EuCl5(THF)]2-和[HO-4,6-di-tBu-C6H2-2-CH2{CH(iPrNCHCHN)}]2+通过氢键作用而形成的空间网状结构的晶体,阴离子中中心金属(Eu)是由五个氯原子以及来自THF的氧原子形成扭曲八面体的构型。     

N-对R苯基氮杂15冠5八钼多酸钠超分子配合物的合成与结构

为研究大环化合物对客体分子的选择性, 合成了通式为[NaL(Et2O)]2Na2Mo8O26的三种新型N-对R苯基氮杂15冠5八钼多酸钠超分子配合物(其中L分别为: N-苯基氮杂15冠5、N-对氯苯基氮杂15冠5和N-对甲苯基氮杂15冠5), 进行了元素分析, 红外光谱与核磁共振等结构参数的表征, 对R基为CH3的标题配合物作了X射线四圆衍射测定, 该晶体属单斜晶系, 空间群为P21/a,a=1.4590(4)nm, b=1.3817(3)nm, c=1.7639(5)nm, β=112.67(2)°, V=3.281(1)nm^3, Mr=2021.3, Dc=2.11g/cm^3,μ=2.37mm^-^1, F(000)=2048, R=0.045和Rw=0.057, 与[Na.(DB18C6)(CH3OH)M6O19和[Na(DB24C8)]2M6O19进行比较,结果表明: 大环化合物不仅对客体金属离子有分子识别性, 而且对与之抗衡的多酸阴离子也具有影响。     

Synthesis and Crystal Structure of a Novel Heptanuclear Ruthenium- and Sodium-containing Polyoxomolybdate [{Na(H_2O)_3}_2{Ru(dmso)_3}_2(MoO_4)_3]·_3H_2O

1 INTRODUCTION Polyoxomolybdates have been of great interest due to their unique structural varieties, associated multitude of properties and applications as catalysis, medicine and material[1, 2]. One of the most impor- tant aspects is the synthesis and investigation of the materials on polyoxomolybdates containing organo- metallic groups[3～5]. Such materials can provide molecular models for heterogeneous catalysis and display cooperative effects or bifunctional catalytic activity[6]. O…     

Synthesis and Structural Characterization of {[Mn(phen)_2(OAc)(H_2O)]ClO_4}_2H_2O

1 INTRODUCTION Chemistry of manganese cluster has become an attractive research field because of the involvement of manganese in several biological redox-active sys- tems[1,2], especially in the oxygen-evolving complex (OEC) of photosystem Ⅱ (PSⅡ) in green plants[3]. It was thought that the coordination environment of Mn in OEC contains O and N donors, and the bind- ing of aqua to the Mn site may be important to the oxidation of aqua for the evolution of dioxygen[4, 5]. In recent …     

Synthesis and Crystal Structure of the Copper Complex {[Cu（CH3COO）2（bbtz）]（H2O）2}n

1 INTRODUCTION The design and synthesis of metal-organic frame- work structures have been extensively studied due to their unexpected properties for potential applications as functional materials as well as the intriguing ar- chitectures and topologies[1～4]. When rigid bifunc- tional ligands are used to connect metal centers, to- pology of the network is usually determined by the coordination geometry of the central metal prefer- ence. Contrary to rigid ligands, the bifunctional fle- xib…     

Synthesis, Crystal Structure and Biological Activity of 2-Chloro-N-{2-fluoro-5-[N-(phenylsulfonyl) phenyl- sulfonamido] phenyl} benzamide

2-Chloro-N-{2-fluoro-5-[N-(phenylsulfonyl)phenylsulfonamido]phenyl}benzamide was synthesized and its crystal structure was also determined by X-ray single-crystal diffraction. The title compound(C25H18C1FN2O5S2) belongs to monoclinic, space group P21/n with a=0.7377(3) nm, b=1.2036(5) nm, c=2.6846(11) nm, β=90.895(9)°,V=2.3833(16) nm3, Mr=544.98, Z=4, Dc= 1.519 g/cm3, μ=0.385 mm-1, F(000)=1120, R1=0.0632, and wR2=0. 1438. Its crystal structure belongs to a novel class that has not been reported yet, and its preliminary herbicidal activity was also tested. Its inhibition rate to seedling growth of barnyard grass reaches 15.1% at 100 μg/mL.     

The Synthesis and Crystallographic Characterization of Heterotrimetallic Linear Complex of [Et_4N][ (Ph_3P)_2{CuS_2WS_2Fe} Br_2]

1INTRoDUCTIONMolybdenum(Tungsten)-copper-sulfurandmolydenum(tungsten)-iron-sulfurcompoundshavebeenstudiedextensivelybecauseoftheirconnectionwithbiologicalprocesses[l,2j.Someheterotrimetalliccomplexeshavebeensynthesized,suchas[NEt'jtPh,p)sAgSzMoSzCu(CN))and[NEt'jtPh,P),AgS,MooCu(CN)jt3i,[l(CH,CH,)'j(PPh,)2{AgS2WS2Cu}(CN)jt4i,[(CH,CH2)4j(PPh,)2{AgS,WOCu}(CN)j('3,butheterotrimetal1iccomplexescontainingtungsten,copper,andironatomshaveseldombeenreported.Onecomplexofthiskindha…     

含三脚架配体及吡啶甲酸根的锰(Ⅱ)配合物的合成及结构表征

本文合成了2种含有吡啶甲酸根的三(2-苯并咪唑亚甲基)胺合锰配合物,并对其进行了红外,元素分析和X-射线单晶衍射测定。结果表明,单核配合物1和2分别具有三角双锥和扭曲八面体的几何构型。在配合物1中,烟酸根阴离子利用一个羧基氧原子和锰离子配位;在配合物2中,邻吡啶甲酸根阴离子采取N,O螯合的配位方式。由于烟酸根和邻吡啶甲酸根的配位方式不同,导致配合物晶体结构中存在不同类型的氢键。配合物1形成了由氢键连接的二维网状结构,而配合物2只能形成由氢键连接成的一维链状结构。     

Transformation and structural discrimination between the neutral {Fe(NO)2}10 dinitrosyliron complexes (DNICs) and the anionic/cationic {Fe(NO)2}9 DNICs

Reaction of Fe(CO)2(NO)2 and sparteine/tetramethylethylenediamine (TMEDA) in tetrahydrofuran afforded the electron paramagnetic resonance (EPR)-silent, neutral {Fe(NO)2}10 dinitrosyliron complexes (DNICs) [(sparteine)Fe(NO)2] (1) and [(TMEDA)Fe(NO)2] (2), respectively. The stable and isolable anionic {Fe(NO)2}9 DNIC [(S(CH2)3S)Fe(NO)2]- (4), with a bidentate alkylthiolate coordinated to a {Fe(NO)(2)} motif, was prepared by the reaction of [S(CH2)3S]2- and the cationic {Fe(NO)2}9 [(sparteine)Fe(NO)2]+ (3) obtained from the reaction of complex 1 and [NO][BF4] in CH(3)CN. Transformation from the neutral complex 1 to the anionic complex 4 was verified via the cationic complex 3. Here complex 3 acts as an {Fe(NO)2}-donor reagent in the presence of thiolates. The EPR spectra of complexes 3 and 4 exhibit an isotropic signal with g = 2.032 and 2.031 at 298 K, respectively, the characteristic g value of {Fe(NO)2}9 DNICs. On the basis of N-O/Fe-N(O) bond lengths of the single-crystal X-ray structures of the {Fe(NO)2}9/{Fe(NO)2}10 DNICs, the oxidation level of the {Fe(NO)2} core of DNICs can be unambiguously assigned. The mean N-O distances falling in the range of 1.214(6)-1.189(4) A and the Fe-N(O) bond distances in the range of 1.650(7)-1.638(3) A are assigned as the neutral {Fe(NO)(2)}(10) DNICs. In contrast, the mean N-O bond distances ranging from 1.178(3) to 1.160(6) A and the mean Fe-N(O) bond distances ranging from 1.695(3) to 1.661(4) A are assigned as the anionic/neutral/cationic {Fe(NO)2}9 DNICs. In addition, an EPR spectrum in combination with the IR nu(NO) (the relative position of the nu(NO) stretching frequencies and their difference Deltanu(NO)) spectrum may serve as an efficient tool for discrimination of the existence of the anionic/cationic/neutral {Fe(NO)2}9 DNICs and the neutral {Fe(NO)2}10 DNICs.     

Synthesis, structural, and magnetic studies on a redox family of tetrametallic vanadium clusters: {VIV4}, {VIII2VIV2}, and {VIII4} butterfly complexes

The synthesis, crystal structures, and magnetic properties are reported for a redox family of butterfly-type tetrametallic vanadium alkoxide clusters, namely [V2(VO)2(acac)4(RC{CH2O}3)2] (R=Me 1, Et 2, CH2OH 3), [V2(VO)2(acac)2(O2CPh)2(MeC{CH2O}3)2] (5), [(VO)4(MeOH)2(O2CPh)2({HOCH2}C{CH2O}3)2] (6), [V4Cl2(dbm)4(RC{CH2OH}3)2] (R=Me 7, Et 8, CH2OH 9), and [V4Cl2(dbm)4(MeO)6] (10). The cluster cores are {VIV4} (6), {VIII2VIV2} (1-5), and {VIII4} (7-10), with examples of both isomeric forms of the of the mixed-valence cores (either VIII or VIV ions forming the butterfly body). Magnetic studies reveal the clusters to be dominated by antiferromagnetic exchange interactions in each case. The magnetic exchange parameters are determined for representative examples of each core type. {VIV4} and {VIII4} have diamagnetic ground states. The two isomeric {VIII2VIV2} types are found to give rise to either an S=0 ground state with a number of low-lying excited states due to competing antiferromagnetic exchange interactions (VIII2 butterfly body) or to a well-isolated S=1 ground state (VIV2 butterfly body).     

新型氧桥和多硫基杂桥联的双核钼硫亚硝基化合物〔(CH_3)_4N〕_2K〔Mo_2OS_2(NO)_2(S_2)_2S_5)·H_2O的合成和晶体结构

本文报导[(CH_3)_4N]_2K[Mo_2OS_2(NO)_2(S_2)S_5]·H_2O的合成和晶体结构。该化合物晶体属于单斜晶系,所属的空间群为P2_1/c。晶胞参数为:a=13.320(2),b=17.377(2),c=13.269(3),β=107.93(2)°,Z=4。在CAD—4四圆衍射仪上,用MoKα射线收录了3576个独立衍射数据(I≥3σ(I))。晶体结构用直接法解出,经Fourier合成和全矩阵最小二乘方修正,最后偏离因子R=0.045。结构分析表明,晶体中Mo—Mo间距为3.421,二钼原子间未成键。Mo原子周围呈近似五角双锥的七配位构型。本结构的特征在于二Mo原子间除双硫桥外还存在氧桥。     

Isomers of a dibismuthane, R2Bi-BiR2 [R = 2,6-(Me2NCH2)2C6H3], and unusual reactions with oxygen: formation of [R2Bi]2(O2) and R'R' 'Bi [R' = 2-(Me2NCH2)-6-{Me2N(O)CH2}C6H3; R' ' = 2-(Me2NCH2)-6-{O(O)C}C6H3

R2Bi-BiR2 [1; R = 2,6-(Me2NCH2)2C6H3], a dibismuthane that exists in different forms in the crystalline state, reacts in air with the formation of the peroxide [R(2)Bi]2(O2) (2) and partial oxidation of the pendant (dimethylamino)methyl groups, yielding the mononuclear bismuth complex R'R' 'Bi (3) [R' = 2-(Me2NCH2)-6-{Me2N(O)CH2}C6H3; R' ' = 2-(Me2NCH2)-6-{O(O)C}C6H3].     

Synthesis and Crystal Structure of a Novel Bimetallic Porphyrin Complex Salt {[MnTPP(CH_3OH)_2]_3Fe(CN)_6}·13H_2O

A novel bimetallic porphyrin complex salt, {[MnTPP(CH3OH)2]3Fe(CN)6}13H2O (TPP = tetraphenylporphyrin), has been synthesized and structurally characterized by X-ray diffraction analysis. The crystal is of trigonal, space group R-3 with a = b = 31.0618(10), c = 11.8366(8) A, Z = 3, V = 9890.3(8) A3, C144H134FeMn3N18O19, Mr = 2641.36, Dc = 1.330 g/cm3, μ(MoΚα) = 0.463 mm-1, F(000) = 4131, R = 0.0525 and wR = 0.1382 for 3045 observed reflections (I > 2σ(I)). The title complex is composed of one [Fe(CN)6]3- anion, three [MnTPP(CH3OH)2]+ cations and thirteen water molecules, which are connected by multiform hydrogen bonds leading to a 3D supramolecular network structure.     

Differentiation of tautomers by ion cyclotron resonance spectrometry: \documentclass{article}\pagestyle{empty}\begin{document}${\rm (CH}_{\rm 3} {\rm)}_{\rm 2} \mathop {\rm N}\limits^{\rm + } {\rm = CH}_{\rm 2} {\rm vs H}_{\rm 3} {\rm C}\mathop {\rm N}\limits^{\rm + } {\rm H = CHCH}_{\rm 3}$\end{document}

Ion cyclotron resonance spectrometry and deuterium labeling have been used to determine that nondecomposing \documentclass{article}\pagestyle{empty}\begin{document}${\rm (CH}_{\rm 3} {\rm)}_{\rm 2} \mathop {\rm N}\limits^{\rm + } {\rm = CH}_{\rm 2}$\end{document} ions do not isomerize to \documentclass{article}\pagestyle{empty}\begin{document}${\rm CH}_{\rm 3} {\rm CH = }\mathop {\rm N}\limits^{\rm + } {\rm HCH}_{\rm 3}$\end{document}.     

Synthesis, Crystal Structure and Photoluminescent Property of a Novel Silver(I) Compound {[Ag(bpp)]_2(Hphth)(NO_3)·(H_2O)_2}_n

Self-assembly of Ag(I) nitrate, 1,3-bis(4-pyridyl)propane (bpp) and phthalic acid monopotassium salt (KHphth) in CH3OH-H2O solution produced the title complex, {[Ag(bpp)]2(Hphth)(NO3)·(H2O)2}n, which was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, and photoluminescent spectrum. Single-crystal X-ray analysis revealed that the complex crystallizes in a monoclinic system, space group P21/c, with a = 15.4174(5), b = 8.6398(2), c = 25.2466(8) , β = 91.072(1)o, V = 3362.34(17) 3, Z = 4, C34H37N5O9Ag2, Mr = 875.43, Dc = 1.729 g/cm3, μ = 1.228 mm-1, F(000) = 1768, the final R = 0.0749 and wR = 0.1580 for 5754 reflections with I > 2σ(I). The Ag atom is coordinated by two N atoms from two bpp molecules in an approximately linear geometry. The Ag(I) ions are linked by the bpp molecules to form one-dimensional zigzag chains propagating along the c axis. The Hphth- and nitrate counter-ions are bridged by solvent water molecules through hydrogen bonds to generate a one-dimensional chain extending along the b axis. Electrostatic interactions between cations and anions, extensive hydrogen bonds and π-π interactions are responsible for the three-dimensional supramolecular structure. In the solid state, the compound exhibits blue photoluminescence with the maximum at 436 nm upon excitation at 344 nm.