光致发光配合物[Au_2(PPh_3)_2(μ-4,4′-bpy)](ClO_4)_2 and [Cu_2(PPh_3)_4(CH_3CN)_2(μ-4,4′-bpy)](BF_4)_2的合成和晶体结构

合成了两个在空气中稳定的Au(Ⅰ )和Cu(Ⅰ )配合物 ,并运用元素分析、红外光谱、荧光光谱和X射线单晶衍射结构表征 ,[Au2 (PPh3 ) 2 (μ 4 ,4′ bpy) ](ClO4 ) 2 (1) (4 ,4′ bpy为 4,4′ 联吡啶 ) ,单斜晶系 ,空间群P2 1c,晶胞参数a=1.2 2 5 5 (4 )nm ,b=0 .9973(3)nm ,c=1.85 0 6 (6 )nm ,β =10 1.732 (5 )°,V =2 .2 145 (11)nm3 ,Z =4,最终偏离因子R =0 .0 430 ,wR =0 .0 937.[Cu2 (PPh3 ) 4(CH3 CN) 2 (μ 4 ,4′ bpy) ](BF4 ) 2 (2 ) ,单斜晶系 ,空间群P2 1c,晶胞参数a =1.34 6 3(3)nm ,b =1.46 81(3)nm ,c =2 .0 6 0 8(4 )nm ,β =10 0 .387(4 )° ,V =4.0 0 6 6 (13)nm3 ,Z =2 ,最终偏离因子R =0 .0 45 0 ,wR =0 .116 3.两个双核配合物都是利用 4,4′ 联吡啶桥联配体 ,形成直线结构 ,直线的两端以PPh3 或CH3 CN为端基 .Au(Ⅰ )为 2配位 ,Cu(Ⅰ )为 4配位 .两个配合物均具有光致发光特性 ,其中配合物 1发光来自MLCT激发态 ,而配合物 2则是受配位金属影响的配体内部发光 .

MoFe3S4单立方烷原子簇研究 Ⅳ.新型的双跨桥六配体单立方烷簇合物 MoFe3S4(μ-Me2NCS2)2(Me2NCS2)4·2CH3 CN 的合成与结构

在二甲胺基二硫代甲酸钠、氯化亚铁及四硫代钼酸铵的自兜反应体系中,以分步结晶法分离出MoFe3S4(Me2NCS2)5·CH2Cl2及MoFe3S4(Me2NCS2)6·2CH3CN等单立方烷簇合物,并测定了后者的结构.它的分子含两个Me2NCS2桥,并具有最高核心氧化态[MoFe3S4]6+.本文报道该化合物的结构特点,指出在自兜反应体系中,可能存在几种不同氧化态的单立方烷原子簇化合物.

三苯基锡(Ⅳ)荒酸衍生物Ph_3SnS_2CN(CH_3)_2的合成、表征、性质及晶体结构

利用三苯基氯化锡和N,N-二甲基荒酸钠反应,合成了三苯基锡(Ⅳ)N,N-二甲基荒酸酯。通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征。用X-射线单晶衍射测定了该化合物的晶体结构。化合物晶体为三斜晶系,空问群Pi,a=1.0402(6)nm,b=1.3126(8)nm,c=1.6645(10),a=778.155(7)°,β=76.422(7)°,γ=85.340(7)°,Z=4,V=2.161(2)nm3,Dc=1.495g/cm3,μ=1.383mm-1,R=0.0460,wR=0.1359。锡原子呈五配位畸变三角双锥构型。

A New Method for the Cleavage of Carbohydrate Benzylidene Acetal by Ceric (IV) Ammonium Nitrate in CH_3CN-H_2O (10: 1)

A new method for the cleavage of carbohydrate benzylidene acetal has been developed using Ceric (YV) ammonium nitrate (CAN) [(NH4)2Ce(NO3)6] in CH3CN-H2O (10/1, v/v).

Electrochemical and Kinetic Behaviors of Fe(Ⅱ) Ion in DMSO, DMF and CH_3CN

The cyclic voltammetry, current time curve at potential step were used to investigate the electrochemical behavior of Fe(Ⅱ) in DMSO, DMF and CH 3CN solutions on Pt cathode. Experimental results indicate that the electroreduction of Fe(Ⅱ) to Fe(0) is irreversible in one step on Pt electrode. The diffusion coefficients of Fe(Ⅱ) in DMSO, DMF and CH 3CN solutions at 298 K were determined to be 2.3×10 -6 , 1.32×10 -6 and 2.5×10 -6 cm 2·s -1 , respectively. The transfer coefficients of Fe(Ⅱ)+2e→Fe(0) in DMSO, DMF and CH 3CN solutions were determined to be 0.11, 0.10 and 0.06, respectively.

Fabrication of SAW Sensor for Detecting Chemical Agent

SAW sensors using five different types of polymer to detect of chemical agents(DMMP,CH_3CN,CH_2Cl_2,DCP) have been fabricated and its gas response characteristics were extensively investigated.The polymers used as the sensing material are polyisobutylene(PIB),polyepichlorohydrin(PECH),polydimethylsiloxane(PDMS),polyisoprene(PIP)and polybutadiene(PBD).Their thin films were coated on quartz substrate by spin coating technique.Three types of simulants gases,dimethylmethylphosphonate(DMMP),acetonitrile(CH_3CN)and dichloromethane(CH_2Cl_2),dichloropentane(DCP)were used as target gases,instead of the real nerve,blood,choking and vesicant agents.After spin coating of PIB and PECH,the substrates were heated to 65℃with N_2 flow for 1 h to remove the cyclohexane and ethylacetate which was used as solvent. PDMS was heated to 75℃with N_2 flow for 2 h to remove the ethylacetate which was used as solvent.PBD and PIP on the substrate were heated to 60℃with N_2 flow for 1 h to remove the benzen which was used as solvent.The sensing characteristics of the SAW sensors were measured by using E-5061A network analyzer.

丙烯腈单体自由基反应及光谱分析的研究

采用密度泛函理论对以偶氮二异丁腈为引发剂形成的丙烯腈单体自由基(CH3)2(CN)C-CH2-(CN)CH的终止方式反应机理进行研究。先用B3LYP/6-31G(d)基组对反应物、偶合中间体、过渡态、歧化产物的几何构型进行优化,并计算了各物种经过零点能校正后的总能量,红外频率和电子结构,同时对过渡态结构进行了验证。研究结果表明,反应物先通过自由基的偶合终止方式形成偶合中间体a,再由此经过氢迁移、裂解等机理得到歧化终止产物P[p1(CH3)2(CN)CCHCHCN+p2(CH3)2(CN)C-CH2-CH2CN]。双自由基发生偶合和歧化终止反应分别形成偶合中间体a和歧化终止产物P均为放热反应,且偶合产物有着更低的能量。反应过程的速控步骤a→TS→P在常温下的速率常数表示为k(298.15K)=2.71×10-59。歧化终止反应随着反应温度的升高易于进行,歧化产物所占的比例也增加。通过对反应过程各物种红外谱图的分析,说明自由基在整个终止反应的化学变化,同时分析了HOMO-LUMO电子密度分布的信息,验证丙烯腈双自由基偶合终止方式和各物种结构的准确性。