离子液体[bmim][PF6]对氧杂蒽酮光解行为的影响

选择氧杂蒽酮(XAN)为探针分子,利用纳秒级瞬态光解技术研究在1-丁基-3-甲基咪唑六氟磷酸盐离子液体([bmim][PF6])以及离子液体与常规溶剂中的光化学行为,探索不同溶剂对氧杂蒽酮激发三线态态(3 XAN*)的最大吸收峰的影响:3 XAN*在纯乙腈(MeCN)中的吸收峰在630nm,而在[bmim][PF6]作溶剂的体系中激发态的吸收峰发生蓝移,而且纯离子液体体系中3 XAN*的产额显著增加。进一步探索离子液体对光诱导3 XAN*与萘(NAP)之间的能量转移及与N,N-二甲基苯胺(DMA)之间的电子转移的影响,结果表明:[bmim][PF6]/MeCN的二元体系中随着[bmim][PF6]浓度的增大,氧杂蒽酮与萘之间的能量转移速率减小,测得在乙腈和纯离子液体中3 XAN*与NAP之间能量转移速率常数分别为1.2×1010 mol·L-1·s-1和1.1×108 mol·L-1·s-1。     

Positive muons in [Co(NH3)6]Cl3 and [Co(ND3)6]Cl3

We have carried out SR experiments on [Co(NH₃)₆]Cl₃ and [Co(ND₃)₆]Cl₃. At 293 K, all the muons implanted into the complexes were in the diamagnetic state. The observed Gaussian-type muon spin relaxation function proved that the internal magnetic field was caused by nuclear dipole moments of the atoms in the complexes. In addition, another exponential-type muon spin relaxation function was observed in [Co(ND₃)₆]Cl₃ below 50 K.     

离子对配合物[Cu(L)n][Ni(dmit)2]的合成与光谱表征

本文首先合成了三种以 Cu2 离子为中心离子的配位阳离子 ,然后将其与配位阴离子 [Ni(dmit) 2 ]2 -组装 ,合成了 3个新型 [Cu Ln][Ni(dmit) 2 ]离子对配合物 ,用元素分析、红外光谱、紫外 -可见吸收光谱对配合物的组成和结构进行了表征     

离子液体[bmim][PF6]与乙腈混合体系中的激光光解研究

以蒽醌(AQ)作为探针分子,利用激光光解技术研究了咪唑型离子液体1-丁基-3-甲基咪唑六氟化磷([bmim][PF6])与乙腈(MeCN)混合体系中的光化学反应行为.研究结果表明,离子液体[bmim][PF6]自身可与激发三线态的蒽醌分子(3AQ*)进行反应,且表观反应速率常数随着[bmim][PF6]/MeCN比例的不同呈现特殊规律性的变化.在离子液体的摩尔分数(xRTIL)为0.06处观察到一个明显的临界点.当xRTIL＜0.06时,表观速率常数随xRTIL的增大而增大;而当xRTIL＞0.06时,表观速率常数随xRTIL的增大而减小.文章给出了[bmim][PF6]/MeCN混合体系中激光诱导化学反应的动力学常数,并初步推测了其反应机理,进一步揭示了离子液体[bmim][PF6]的一些新的光化学特性.     

2-(2-苯并噁唑啉酮-3-甲基)-6-芳基-咪唑[2,1-b][1,3,4]噻二唑的NMR谱研究

许多文献已报道,含有咪唑[2,1-b][1,3,4]噻唑环的衍生物具有抗癌、抗结核、抗菌、抗真菌、抗惊厥、止痛等活性. 该文合成了一个新的在医药方面具有潜在应用价值的咪唑[2,1-b][1,3,4]噻二唑衍生物,即2-(2-苯噁唑啉酮-3-甲基)-6-苯基-咪唑[2,1-b][1,3,4]噻二唑,并利用2D NMR技术对其¹H NMR 和¹³C NMR谱进行了全归属.      

Lattice dynamics,phase transitions and spin relaxation in [Fe(C5H5)2] PF6

The organometallic compound ferrocenium hexafluorophosphate, [Fe(C₅H₅)₂] PF₆, has been studied by Mössbauer spectroscopy in the past, mainly to determine the crystal structure at high temperatures. Here we present studies at 95 K to 305 K and analyze the spectra in terms of spin relaxation theory which yields accurately the hyperfine interaction parameters and the spin-spin and spin-lattice relaxation rates in this paramagnetic compound. The spectral area under the resonance curve yields the recoil free fraction and thus the mean square of the vibration amplitude <x²>. One observes a large discontinuity in the slope of <x²> versus T at ?210 K, indicative of a phase transition. The analysis of the spectra proves that the quadrupole interaction is small but certainly negative, ½e²qQ = -0.12(2) mm/s, and causes the asymmetry observed in the spectra. The detailed analysis yields also, for the first time, the fluctuating effective magnetic hyperfine field, H _eff = 180(50) kOe.     

配合物Zn3(NCS)6(L1)6(NO3)2及Ni3(NCS)6(L2)6(NO3)2的合成、光谱表征及荧光性质

以去离子水为溶剂,合成了以Zn2+及N12+为中心,以L1,L2[L1=4-氨基-3,5-二甲基-1,2,4-三唑,L2=4-氨基-1,2,4-三唑]及硫氰酸根为配体的两种配合物,对其进行了元素分析、金属离子络合滴定、摩尔电导测定,确定了配合物组成分别为Zn3(NCS)6(L1)6(NO3)2及Ni3(NCS)6(L2)6(NO3)2,同时对两种配合物做了红外光谱、紫外光谱及荧光光谱的测试表征.荧光光谱的测试表明两种配合物均在415 nm有一强的荧光发射峰,且镍配合物的荧光要明显强于锌配合物,两种配合物有望成为蓝光发光材料.     

[Ru(bpy)2L]2+、 [Ru(phen)2L]2+(L=pytp,pztp)电子结构与抗癌活性研究

对配合物[Ru(bpy)2L]2+、[Ru(phen)2L]2+(L=pytp,pztp),用密度泛函(DFT)法,在B3LYP/LanL2DZ水平上进行理论计算研究.探讨了配合物的电子结构与其抗癌活性的关系,主配体上N原子的增加有利于配合物与DNA的作用,增加配合物的抗癌活性.计算结果显示,对于配合物I～IV,其LUMO轨道能量次序为εI>εII和εIII>εIV;其LUMO的电子云主要分布在主配体上,且分布的含量有I相似文献   

The thermal metal-insulator phase transition in (EDO-TTF)2PF6

ABSTRACT

The thermal metal-insulator phase transition in the π-stacked (EDO-TTF)₂PF₆ charge transfer salt is of the Peierls type. It is related to geometrical reorganisations and charge ordering phenomena. We report that dimerising displacements are involved in the mechanism of this transition. By using periodic quantum chemical calculations, we find a double well potential in which dimerisation and charge localisation become manifest. By analysing the nuclear wavefunctions we discuss the mechanism of the phase transition in terms of thermal fluctuations.     

Time integral and time differential Mössbauer measurements on [57Co/Mn(bipy)3](PF6)2

The Mössbauer emission spectra of nucleogenic iron(II) complexes with a low spin (LS) ground state show two metastable iron(II) high spin (HS) states at low temperatures. In order to identify these metastable HS states, the compound [⁵⁷Co/Mn(bipyridine)₃](PF₆)₂ has been studied by time differential Mössbauer emission spectroscopy (TDMES) and optical lifetime measurements of excited electronic states in the corresponding Fe-doped Mn compound. The lifetime of one of the HS states of the nucleogenic iron(II) determined by TDMES has been measured to be the same as the lifetime of the laser-excited iron(II) electronic state.     

EPR of Mn2+ in single crystals of [Zn(H2O)6]SnF6 and [Co(H2O)6]SnF6; Co2+ spin-lattice relaxation time

EPR studies have been carried out in Mn²⁺-doped single crystals of [M(H₂O)₆]SnF₆ (M  Zn, Co) at different temperatures using X-band microwave frequency. Mn²⁺ has been found to substitute for Zn²⁺ or Co²⁺ exhibiting a unique magnetic complex with z-axis directed long the c-axis of the crystals. Observation of resolved Mn²⁺ spectrum in [Co(H₂O)₆]SnF₆ and broadening of the resonance lines on cooling the crystals have been explained on the basis of host spin-lattice relaxation narrowing. The T₁ of Co²⁺ has been estimated to be ≈ 1.8 × 10⁻¹² s at 293 K.     

Electrical properties and conduction mechanism of [N(C2H5)4][N(CH3)4]CuCl4 compound

The [N(CH₃)₄][N(C₂H₅)₄]CuCl₄ single crystal has been synthetized in order to determinate the temperatures transition and to study the electrical properties and the conduction mechanism. At room temperature, this compound crystallizes in the tetragonal system with P-42₁m space group. The calorimetric study shows three anomalies at 248, 284 and 326 K. Electrical conduction and dielectrical relaxation mechanisms at various frequencies and temperatures were analyzed by impedance spectroscopy and the equivalent circuit based on the Z-View-software was proposed. The variation of f_p relaxation determinate by the modulus study and σ_dc specific to the AC conductivity as a function of temperature and confirm the all transitions for our sample. The values of the activation energy are determined and compared by those, which are found in the similar compound. Frequencies dependence of alternative current (AC) conductivity is interpreted in terms of Jonscher's law and the conduction mechanisms for each phase are determined with the Elliot's theory.     

[{Na(18-C-6)}2(H2O)][Ni(i-mnt)2]的合成与结构分析

研究了18-冠-6与Na2[Ni(i-mnt)2]{i-mnt=异丁二腈烯二硫醇阴离子,[S2C2(CN)2]2-}的反应,得到的配合物[{Na(18-C-6)}2(H2O)][Ni(i-mnt)2](1),通过元素分析、红外光谱、X射线单晶衍射进行了结构分析。配合物为三斜晶系,空间群P-1。晶体学结构数据:a=1.0991(12)nm,b=1.1011(12)nm,c=1.1305(12)nm,α=70.44(2)°,β=87.44(2)°,γ=62.552(19)°,V=1.134(2)nm3,Z=1,F(000)=488,R1=0.3771,wR2=0.1497。(1)中的[Ni(i-mnt)2]基团通过配体i-mnt的氮原子与两个[Na(18-C-6)]基团之中的钠原子成键,形成稳定的中性配合物。