A Doubly Bridged Bis(phenylethynyl)benzene: Different from a Twisted Tolan

The synthesis of a doubly bridged 1,4-bis(phenylethynyl)benzene is reported. The target displays photophysical properties, distinctly different from that of its congeners, the singly bridged tolans. Quantum-chemical calculations suggest a lack of planarization of the bridged bis(phenylethynyl)benzene in the first excited state.     

Novel System for the Synthesis of Nitriles from Aldehydes Using Aqueous Ammonia and [Bis(Trifluoroacetoxy)iodo]benzene

A simple and mild method for the conversion of varieties of aldehydes to the corresponding nitriles using aqueous ammonia and trivalent hypervalent iodine reagent, [bis(trifluoroacetoxy)iodo]benzene, at room temperature is discussed. Advantages of this system are short reaction time, easy workup, and moderate to good yields.     

Synthesis and Crystal Structure of 1,2-Bis（2-benzimidazolyl）benzene

The title compound C6H4(C7H5N2)2 was prepared by the condensation of o-phenylenediamine with o-phthalic acid and characterized by elemental analysis, IR, UV and ^1H NMR spectra, and its structure was determined by single-crystal X-ray diffraction,showing the compound molecule belongs to (72 point group. A ID chain structure was formed by the intermolecular hydrogen bonds (N(2)H…N(I)).     

手性二噁唑啉吡啶铁和镍配合物的制备与表征

Tridentate bis(oxazolinylpyridine)(1) reacted with nickel chloride or ferrous chloride in anhydrous ethanol to form bis(oxazolinylpyridine) Nickel(Ⅱ) and Iron(Ⅱ) complexes. The stable solid complexes were characterized with IR， UV， MS， XPS and elemental analysis. No stable complexes were formed with bidentate bis(oxazoline)(2) ins- tead of bis(oxazolinylpyridine).     

含双咪唑配体的锌配位聚合物的晶体结构、荧光性质及抑菌性能研究

本文报道了一个基于双咪唑配体的锌配位聚合物[Zn(oxa)(bbi)]n(1)(oxa=草酸,bbi=1,1′-(1,4-丁二基)双咪唑),并对该化合物进行元素分析、红外和X-射线单晶衍射分析。结果表明标题化合物通过配位键和π-π堆积作用力形成了一个由(4,4)拓扑形状的二维网络组成的具有大孔洞的三维金属有机框架结构。除此之外,测定了配合物1的荧光发射光谱并对其微生物抑菌性能进行了初步研究。     

Synthese von Mono- und Bis(silyl)hydroxylaminen

Synthesis of Mono- and Bis(silyl)hydroxylamines Silylamines reacts with hydroxylaminehydrochlorid to give the monosilylhydroxylamines: R₂FSiONH₂ (R = CMe₃ 1 ), R₂R′SiONH₂ (R = CMe₃, R′ = Me 2 ), R₂(NH₂)SiONH₂ (R = CMe₃ 3 ). The reaction of 1 in the present of HCl-acceptors or the reaction of lithiated 1 with Me₃SiCl or F₂Si(CMe₃)₂ leads to the formation of bis(silyl)hydroxylamines, (Me₃C)₂FSiONHSiMe₃ 4 , and (Me₃C)₂FSiONHSiF(CMe₃)₂ 5 . The lithium derivatives of Me₃SiONH₂ and 2 react with fluorosilanes to the bis(silyl)hydroxylamines: Me₃SiONHSiFRR′ (R = R′ = CMe₃, 6 , R = CMe₃, R′ = F 7 , R = R′ = NMeSiMe₃ 8 ), (Me₃C)₂MeSiNHOSiFRR′ (R = CMe₃, R′ = F 9 , R = (Me₃C)₃C₆H₂, R′ = F 10 , R = R′ = CMe₃ 11 , R = R′ = CHMe₂ 12 ). The bis(silyl)hydroxylamines 4 and 6 are structure isomers.     

氧化蒽基二吲哚基甲烷显色现象的研究

通过两步反应合成了两个具有显色特性的化合物:氧化2-蒽基二吲哚基甲烷(2-AnBIM)和氧化9-蒽基二吲哚基甲烷(9-AnBIM).比较了它们在不同非质子溶剂、不同阴离子和酸性环境中的光谱行为.在非质子溶剂中,发现这两种化合物仅在CCl₄中有很大的红移,该红移现象的本质尚不清楚.浓度效应与NMR证据均表明在CCl₄中化合物存在基于氢键的分子间相互作用.在含有不同阴离子的乙腈中,2-AnBIM对F^-离子有选择性响应,而9-AnBIM则对F^-、Cl^-和Ac^-等阴离子均有响应;在质子性溶剂中二者均只对HSO₄^-有选择性响应.2-AnBIM与9-AnBIM在77 K下有荧光发射,而平面性较好的2-AnBIM具有较低的发射能级与较强的发光效率.室温下二者均无明显的荧光发射,这可能与激发态下快速的质子转移导致分子共轭、共平面程度降低有关.     

Syntheses and Structures of Three Copper Coordination Polymers Based on Bis(triazol‐1‐ylmethyl)benzene

Three copper(II) coordination polymers [Cu(mbtz)₂(NCS)₂]_n ( 1 ), [Cu(mbtz)₂Cl₂]_n ( 2 ) and [Cu(mbtz)(btec)_0.5]_n ( 3 ) (mbtz=1,3‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene, btec=1,2,4,5‐benzenetetracarboxylate) were synthesized. In 1 and 2 , two mbtz ligands are wrapped around each other and are held together by Cu(II) atoms to form one‐dimensional double chain. In 3 , each btec ligand connects four Cu(II) atoms through its four carboxylate groups, resulting in a planar two‐dimensional [Cu(btec)_0.5]_n network. The Cu(II) atoms are further coordinated mbtz ligands to fulfil their coordination geometry and construct new [Cu(btec)_0.5(mbtz)]_n network. 2 and 3 further form the three‐dimensional network through the π···π stacking interactions between the mbtz ligands. The thermal stabilities of 1 , 2 and 3 were measured.     

Quantitative Photoswitching in Bis(dithiazole)ethene Enables Modulation of Light for Encoding Optical Signals

Using one ray of light to encode another ray of light is highly desirable because information in optical format can be directly transferred from one beam to another without converting back to the electronic format. One key medium to accomplish such an amazing task is photoswitchable molecules. Using bis(dithiazole)ethene that can be photoswitched between its ring‐open and ring‐closed states quantitatively with excellent fatigue resistance and high thermal stability, it is shown that quantitative photoreversibility allowed the photoswitching light to control other light travelling through the photoswitchable medium, a phenomenon of transferring information encoded in one light ray to others, thus imparting photo‐optical modulation on the orthogonal light beam.     

Bis(tetramethylammonium), bis(tetrabutylammonium), and bis(tetraphenylarsonium) dihydrohexaoxoxenonates(VIII)

Bis(tetramethylammonium), bis(tetrabutylammonium), and bis(tetraphenylarsonium) dihydrohexaoxoxenonates(VIII) were obtained in an aqueous solution and in acetonitriie. The rate constants of their decomposition were determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 184–185, January, 1995.This work was carried out with financial support from the International Scientific Foundation (Grant REI 000).     

二(o-溴苄基)锡双(二乙基二硫代氨基甲酸)酯和二(o-氯苄基)锡双(吡咯啶二硫代氨基甲酸)酯的合成、结构及体外抗癌活性研究

二(o-溴苄基)二溴化锡和二(o-氯苄基)二氯化锡分别与N,N-二乙基二硫代氨基甲酸钠和吡咯啶二硫代氨基甲酸钠反应,合成了二(o-溴苄基)锡双(二乙基二硫代氨基甲酸)酯(1)和二(o-氯苄基)锡双(吡咯啶二硫代氨基甲酸)酯(2)。用X-射线单晶衍射测定了两个化合物的晶体结构,测试结果表明:化合物1的晶体为单斜晶系,空间群P21/c,晶体学参数a=1.827 36(4)nm,b=0.900 60(2)nm,c=1.988 41(5)nm,β=114.878 0(10)°,V=2.968 71(12)nm3,Z=4,Dc=1.690 g·cm-3,μ(Mo Kα)=38.50 cm-1,F(000)=1 496,R1=0.051 6,wR2=0.154 6。化合物2的晶体为单斜晶系,空间群C2/c,晶体学参数a=2.241 28(4)nm,b=0.818 78(2)nm,c=1.542 69(3)nm,β=106.787 0(10)°,V=2.710 37(10)nm3,Z=4,Dc=1.623 g·cm-3,μ(Mo Kα)=14.65 cm-1,F(000)=1 336,R1=0.022 9,wR2=0.056 5。晶体中锡原子呈六配位畸变八面体构型。对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。测定了配合物的热稳定性和体外抗癌活性。     

Synthesis and Crystal Structure of a Tetranuclear Silver Complex with Bis（diphenylphosphino） amine-dioxide as a Tridentate Ligand

1 INTRODUCTION The coordination chemistry of the nitrogen-contai- ning diphosphine ligand bis(diphenylphosphino)ami- ne (Ph2PNHPPh2) has recently received much atten- tion because the P atoms can bridge metal centers in μ-bonding mode to form bi- or polynuclear complex- es[1~10]. It has been shown that the acidity of N–H proton would promote functionalization on the ligand backbone[4, 5, 11]. Although a few complexes contain- ing deprotonated tridentate Ph2PNPPh2 have been synthesi…     

含双二苯基膦甲烷铜(Ⅰ)配合物的研究进展

本文概述了含双二苯基膦甲烷铜(Ⅰ)配合物的化学进展,总结了配合物的合成方法:置换法、还原法、电化学方法和直接加成法,全面论述了双核、三核、多核和异核配合物的结构特征,探讨了该类配合物的重要荧光性质。     

Theoretical study on second-order nonlinear optical properties of unsymmetric bis (phenylethynyl) benzene series derivatives

On the basis of ZINDO methods, according to the sum-overstates (SOS) expression, the program for the calculation of the second-order nonlinear optical susceptibilities βijk and βμ of molecules was devised, and the structures and nonlinear optical properties of unsymmetric bis (phenylethynyl) benzene series derivatives were studied. The influence of the molecular conjugated chain lengths, the donor and the acceptor on βμ was examined.     

离子负载的双(三氟乙酰氧基)碘苯对乙酰苯胺类化合物的乙酰氧基化反应

制备了1种新的含有酰胺键的离子负载的双(三氟乙酰氧基)碘苯固体试剂--1-甲基-3-[4鄄(双三氟乙酰氧基碘)苯甲酰胺基乙基]咪唑四氟硼酸盐. 该试剂无吸湿性, 在空气中长期放置不变质. 研究了1种离子负载的二(乙酰氧基)碘苯试剂和3种离子负载的双(三氟乙酰氧基)碘苯试剂对乙酰苯胺的对位乙酰氧基化反应. 结果表明, 离子负载的二(乙酰氧基)碘苯试剂氧化能力较弱, 乙酰氧基化产物产率较低; 含有酰胺键的2种离子负载的双(三氟乙酰氧基)碘苯试剂不发生乙酰氧基化反应; 而1-甲基-3-[4-双(三氟乙酰氧基)碘苯甲基]咪唑四氟硼酸盐是理想的氧化剂. 以1-甲基-3-[4-双(三氟乙酰氧基)碘苯甲基]咪唑四氟硼酸盐为氧化剂, 室温下乙酰苯胺及其衍生物与乙酸可区域选择性地发生乙酰氧基化反应, 产率较高. 回收后的离子负载的碘苯容易再生成试剂, 而再生试剂的乙酰氧基化反应活性几乎保持不变.     

A Promising Thermodynamic Study of Hole Transport Materials to Develop Solar Cells: 1,3-Bis(N-carbazolyl)benzene and 1,4-Bis(diphenylamino)benzene

The thermochemical study of the 1,3-bis(N-carbazolyl)benzene (NCB) and 1,4-bis(diphenylamino)benzene (DAB) involved the combination of combustion calorimetric (CC) and thermogravimetric techniques. The molar heat capacities over the temperature range of (274.15 to 332.15) K, as well as the melting temperatures and enthalpies of fusion were measured for both compounds by differential scanning calorimetry (DSC). The standard molar enthalpies of formation in the crystalline phase were calculated from the values of combustion energy, which in turn were measured using a semi-micro combustion calorimeter. From the thermogravimetric analysis (TGA), the rate of mass loss as a function of the temperature was measured, which was then correlated with Langmuir’s equation to derive the vaporization enthalpies for both compounds. From the combination of experimental thermodynamic parameters, it was possible to derive the enthalpy of formation in the gaseous state of each of the title compounds. This parameter was also estimated from computational studies using the G3MP2B3 composite method. To prove the identity of the compounds, the ¹H and ¹³C spectra were determined by nuclear magnetic resonance (NMR), and the Raman spectra of the study compounds of this work were obtained.     

刚性4-取代双三唑配体构筑的三个锌配合物的合成和荧光

在室温下合成了3个新的配位聚合物{[Zn(4?Nbdc)(btx)]·2H₂O}_n(1·2H₂O)、[Zn(btx)_1.5(1,3?bdac)]n(2)和{[Zn(mbtx)(1,3?bdc)(H₂O)₂]·H₂O}_n(3)(btx=1,4?二(4H?1,2,4?三唑)苯,mbtx=1,3?二(4H?1,2,4?三唑)苯,4?Nbdc=4?硝基邻苯二甲酸根,1,3?bdac=间苯二乙酸根,1,3?bdc=间苯二甲酸根),测试了配合物的单晶结构,并从元素分析、红外和粉末衍射等方面进行表征。单晶X射线衍射表明,配合物1是二维(4,4)网格结构,配合物2和3都是一维链状结构。配合物2中的π?π作用将一维链连接成三维网格结构。在配合物3中,分子间氢键将一维链连接成二维网格,2套二维网格在分子间氢键的作用下相互穿插得到2D+2D→2D的网格结构。同时,还研究了3个配位聚合物的荧光和热稳定性。     

具有聚集荧光增强性质的双(4-二乙氨基水杨醛)缩偶氮二甲酰肼二丁基锡的合成和晶体结构

在甲醇溶液中,卡巴肼、(4-二乙氨基)水杨醛和二乙酸二丁基锡"一锅法"反应,合成了一个新颖的基于双(4-二乙氨基水杨醛)缩偶氮二甲酰肼(L)的七配位有机锡配合物[Sn(L)(n-butyl)_2]n(T)。经元素分析、IR、(1H,119Sn,13C)NMR和X射线衍射晶体结构表征,T的晶体属单斜晶系C2/c空间群,中心锡周围由双(4-二乙氨基水杨醛)缩偶氮二甲酰肼的O,N配位原子占据赤道位置和2个丁基占据顶端位置形成畸变五角双锥构型。通过烯醇式氧原子的桥联配位作用,T向一维带状无限扩展产生"竹筏状"超分子结构。配合物T在二甲基甲酰胺、四氢呋喃、乙醇、甲醇和甲苯有机溶剂及其有机溶剂-水混合物中具有强荧光发射峰,当含水量的体积分数在0～10%(V/V)时具有良好的聚集荧光增强效应,含水量大于10%(V/V)时发生荧光淬灭。     

影响双(2-丁氧羰基-3,4,6-三氯苯基)草酸酯化学发光体系的因素

过氧草酸酯类化学发光是一类以多氯代水杨酸酯与草酰氯反应生成的草酸酯、过氧化氢和荧光剂为主要组成的化学发光体［１，２］．它除了具有发光效率高，强度大，寿命长的特点外，还可以通过选择荧光剂调节发光的颜色．采用这类发光体系可制成多种化学光源．在草酸酯和荧光...