Tb,Eu,La氨基苯甲酸邻菲啰啉配合物的研究

本文报导了Tb,Eu,La与邻氨基苯甲酸(o-AA)或N-苯基邻氨基苯甲酸(N-PAA)及邻菲啡啰啉(Phen)形成的固态三元配合物。通过元素分析,热谱分析和摩尔电导测定确定该类配合物的组成为Ln(Phen)(L)₃(Ln=Tb、Eu、La,L=o-AA或N-PAA),考察了这类配合物的红外光谱、UV吸收光谱、核磁共振谱和x光电子能谱,确定其配位形式,并讨论了它们的发光性质。     

固体化合物YbCl~2和AYbI~3(A=Cs,Rb, K)中^1^7^1Yb NMR谱 及核磁屏蔽性质

首次在室温下测定了^1^7^1Yb在YbCl~2中的化学位移、化学位移各向异性、自旋-晶格弛豫时间、自旋-晶格弛豫时间的各向异性,计算出自旋-自旋弛豫时间。根据TMS(^1H)的绝对屏蔽常数,计算了^1^7^1Yb在YbCl~2和在AYbI~3(A=K,Rb,Cs)中的平均绝对屏蔽常数(σ~i~s~o),逆磁绝对屏蔽常数(σ~i~s~o^d)和顺磁绝对屏蔽常数(-σ~i~s~o^p),并且对^1^7^1Yb的各项屏蔽常数与结构之间的关系进行了讨论。     

Homopolymerization of ω‐Styryl‐Polystyrene Macromonomers in the Presence of CpTiF3/MAO

Summary: ω‐Styryl‐polystyrene macromonomers were synthesized by anionic induced deactivation reactions. Their homopolymerization in the presence of a fluorinated half‐sandwich metallocene catalyst (CpTiF₃/MAO) was investigated. In spite of the intrinsic lower reactivity of these macromonomers with respect to the micromolecular monomer, coordination homopolymerization was possible. The influence of several experimental parameters on the polymerization yield and degree could be demonstrated. In most cases, under identical experimental conditions, higher polymerization yields and degrees were observed with respect to the CpTiCl₃/MAO catalyst.

The synthesis of p‐polystyryl‐substituted styrene derivatives by the homopolymerization of ω‐styryl‐polystyrene macromonomers in the presence of CpTiF₃.     

Yb：YAG晶体中的荧光浓度猝灭现象

在Ｙｂ：ＹＡＧ晶体中发现浓度猝灭现象,对猝灭机制进行了分析研究,指出退火前晶体的荧光浓度猝灭现象主要由Ｙｂ＾２＋、色心和由此产生的晶格畸变所致高掺杂浓度时痕量稀土杂质离子的存在也将导致浓度猝灭,确定了Ｙｂ：ＹＡＧ晶体中Ｙｂ＾３＋的理想掺杂浓度。     

掺Yb双包层光纤激光器波长调谐输出

采用调节腔损耗以调节阈值的方法实现了掺Yb双包层石英光纤激光器的波长调谐输出 调谐范围达50nm 、步长约2nm 当损耗增大阈值升高时,激射波长向短波方向漂移.利用石英中Yb³⁺的能级结构和光谱特性对以上规律进行了定性解释.     

De–excitation of compound nuclei with A around 56: reduction of the emission barriers for protons and alpha particles

This paper contributes to the discussion on the phenomena of the enhanced emission of low–energetic charged particles during compound nuclei decay. The decay of compound nuclei ⁵²Fe, ⁵⁶Ni, and ⁵⁹Cu was studied. Energy spectra and emission angles of evaporated charged particles were measured in coincidence with gamma rays to determine the corresponding evaporation residue nucleus. Additionally, evaporation residue distributions were determined with the Munich rf recoil spectrometer. In this way, detailed channel–specific evaporation data were obtained for theoretical analysis. We extracted evaporation barriers and compared them with corresponding fusion barriers. The main result was revealed to be a lowering of the evaporation barrier for protons and alpha particles relative to the fusion barriers. But the observed effect is not as intensive as reported in recent studies. Received: 15 June 1998 / Revised version: 5 November 1998     

A new high-spin isomer in 145Sm

A new high-spin isomer in ¹⁴⁵Sm was observed by in-beam γ-ray spectroscopy with the reaction ¹²²Sn(²⁷Al,3np) at 127 MeV performed at the Nordball multi-detector array in Roskilde. The excitation energy of the isomer was determined to be E _x= 11147 keV, and using the generalized centroid-shift method its half-life was found to be T _1/2= (7.4 ± 1.0) ns. Received: 23 October 1998     

新型氮杂大环化合物的研究2: 四吡唑类卟啉大环化合物的合成 及配位性能

报道了几种四吡唑类卟啉大环化合物的合成及其对Ru^2^+离子的配位性能。结果表明,配体环中4个sp^2杂化N原子均参与对Ru^2^+配位,形成一个近似配位平面,另有两个相同或不同的轴向配体位于平面上下,形成稳定的八面体配位结构。根据轴向配体的配位稳定性可方便地将其进行交换。     

锌卟啉轴向配合物的光谱特性及配位二聚体分子内的能量传递

通过轴向配位作用构造了ZnTPP-H₂(m-py)TPP卟啉二元体系,研究了配位二聚体的可见吸收光谱和荧光发射光谱特性,考察了二聚体分子内的能量传递过程,观察到能量从激发态ZnTPP^*流向H₂(m-py)TPP。作为对比,研究了ZnTPP-py体系的可见吸收光谱和荧光发射光谱。轴向配位的吡啶引起了ZnTPP荧光光谱明显红移,没有分子内的能量转移过程发生。用吸收光谱和荧光光谱方法计算了加合反应的平衡常数,得到了基本一致的结果。     

Thermodynamic study of axial coordination reaction of zinc porphyrin with metal Schiff base and imidazole complex

A thermodynamic study is reported for the coordination reaction of ZnT ( m-X)PP derivatives (X = NO2, Cl, OCH3, H or CH3) with various ligands L (L= imidazole (Im), 2-methylimidazole (MeIm), clotrimidazole (CIM), imidazole-4-carboxaldehyde (4-CHOIm), unsymmetrical tetradentate copper Schiff base, CuIm(p-Cl), CuIm(p-Br), and nickel Schiff base, NiIm(p-Cl)), in dichloromethane solvent. Conversion of the four-coordinated ZnT( m-X)PP to the five-coordinated species is followed and isosbestic behavior is exhibited in the region among 450 and 700 run. The reaction of a copper(Ⅱ) or nickel(Ⅱ) imidazolate Schiff base with ZnT(m-X)PP results in the formation of an imidazolate bridged heterobinuclear complex. The stoichiometric number is unity for all axial ligands. The equilibrium constants were determined using the β band of ZnT( m-X)-PP in the 293-308 K range by the method of Rose and Drago. It increases with decrease in temperature, and △H0 < 0, △S0 < 0. The stronger the nucleophilic ability of the axial