煤液化沥青烯的荧光光谱表征及缔合结构研究

通过分子荧光光谱和紫外可见吸收光谱表征、研究了煤液化沥青烯结构及缔合行为。结果发现：煤液化沥青烯属于萘环结构为主的芳香化合物混合体系,具有强的荧光效应;溶剂与沥青烯分子能够形成激态复合物,导致沥青烯荧光峰红移和荧光猝灭;沥青烯分子间存在非共价键缔合作用,高温液化沥青烯芳香度高,缔合作用强;沥青烯分子间缔合属于逐步缔合过程,不存在“临界缔合浓度”,其表观荧光强度随浓度变化的临界浓度受激发波长影响。     

Chemical shift driven geometry optimization

A new method for refinement of 3D molecular structures by geometry optimization is presented. Prerequisites are a force field and a very fast procedure for the calculation of chemical shifts in every step of optimization. To the energy, provided by the force field (COSMOS force field), a pseudoenergy, depending on the difference between experimental and calculated chemical shifts, is added. In addition to the energy gradients, pseudoforces are computed. This requires the derivatives of the chemical shifts with respect to the coordinates. The pseudoforces are analytically derived from the integral expressions of the bond polarization theory. Single chemical shift values attributed to corresponding atoms are considered for structural correction. As a first example, this method is applied for proton position refinement of the D-mannitol X-ray structure. A crystal structure refinement with 13C chemical shift pseudoforces is carried out.     

Synthesis,Crystal Structure and Calculated β Value of a Tetrahedral Zinc (II) Complex——Zn(2-NH_2py)_2Br_2

1 INTRODUCTION Coordination chemistry has been playing an important role in nonlinear optical (NLO) materi- als [1~3] in recent years. It has been found that tetrahedral or square pyramidal molecular configurations are useful for designing transparent second-harmonic generation (SHG) materials from coordination compounds[4]. It has also been reported that the pyridyl-based metal complexes can exhibit SHG effects[5]. Recently, we have successfully synthesized a new coordination compoun…     

Crystal Structure of (6S,9S,13R,14S)-7,8-Didehydro-3,7-dimethoxy-17-methylmorphinan-4,6-diol

1 INTRODUCTION (9S,13R,14S)-7,8-Didehydro-3,7-dimethoxy-4-hydroxy-17-methylmorphinan-6-one I is an impor- tant natural product that was used to ease pain, decrease blood pressure and diminish inflammation. In order to study the stereochemistry of the reduction of I with potassium boronhydride, the crystal structure of the title compound II was determined by X-ray diffraction method. 2 EXPERIMENTAL 2. 1 Instrument The melting point was measured on a Yanagimoto MP-500 apparatus…     

Crystal Structure and Characterization of a Dye with Two-photon Pumoed Frequency-upconverted Lasing Properties

The title compound, trans-4-[ p-( N-ethyl-N-(hydroxyethyl ) amino) styryl ]-N-methylpyridiniumtetraphenylborate (abbreviated as ESMT, C46H49N4OB) crystallizes in a space group P1- with a= 0. 983 23 (15)nm, b=1.410 73(16) nm, c=1.54 21(12) nm, a=95.252(13)°, β=91.959(17)°, γ= 107.421(12)°, Z=2, F(000)=712, μ= 0.1 mm-1 Mo Ka radiation, R=0. 093 8. The result shows that the cation of themolecule almost lies in one plane, the hydroxyethyl group is perpendicular to the plane, the anion takes a slightdistorted tetrahedral geometry. Also the thermal stability, two-photon fluorescence, two-photon pumped lasingproperty for the title compound were studied.     

环四甲撑四硝胺(HMX)结构和性质的DFT研究

用密度泛函理论(DFT)B3LYP方法,取6-31G基组,求得环四甲撑四硝胺分子的几何构型、电子结构、 IR谱和298～1200 K的热力学性质.全优化几何构型和电子结构均具有Ci对称性.在相邻原子之间以N-NO2键的Mulliken集居数最小,表明其间电子分布较少,预示其为热解和起爆的引发键.IR谱与实验结果良好相符.     

环五甲撑五硝胺(CRX)结构和性质的DFT预示

用密度泛函理论(DFT)B3LYP方法,在6-31G*基组水平下,全优化计算了环五甲撑五硝胺(CRX)的分子几何和优化构型下的电子结构.环C-N键长为0.144～0.148 nm, N-NO2键长为0.139～0.142 nm; CRX的最高占有MO(HOMO)能级和最低未占MO(LUMO)能级之间的差值ΔEg(5.2054 eV)较大,预示CRX较稳定.基于简谐振动分析求得IR谱频率和强度.运用统计热力学方法,求得在200～1200 K的热力学性质C0p,m、 S0m和H0m.还运用Kamlet公式预示了它的爆速和爆压分别为9169 m/s和37.88 GPa.     

Synthesis and crystal structure of a new one-dimensional system with end-to-end single dicyanamide bridges between nickel(II) centres

The complex [Ni(tn)₂{N(CN)₂}]ClO₄ (tn=trimethylenediamine) has been synthesized and the structure has been determined. The complex forms a one-dimensional chain structure via the bidentate bridging ligand dicyanamide. A two-dimensional networks is formed via interchain hydrogen bond interactions.