Theoretical Design of High-spin Organic Molecules with —^＊N—S— as a Spin-containing Fragment and Heterocycle as End Groups

IntroductionDesigns and syntheses of organic molecules withvery high-spin ground states have been a topic of greatinterest[1—8].One of the rational approaches to desig-ning high-spin molecules,which has been proposedand studied by several groups[9,10],in…     

四（对-羟基苯基）卟啉氧合配合物的室温固相合成，表征及氧合能力

采用固相反应合成了四羟基苯基卟啉与与Fe^2＋,Co^2＋金属离子的配合物,在室温下,将其与分子O2作用,提纯后得到两种固态氧合配合物．通过元素分析、红外光谱（IR）、核磁共振氢谱（^1HNMR）、电导、热分析（TG／DTA）、紫外光谱（UV）等测试手段确定了氧合配合物的组成为[Co·THPP·O2]（NO3）2·2H2O、[Fe·THPP·O2]Cl2·2H2O]，可知1mol配合物吸收了1molO2,采用失重法测定了氧合配合物中的配位氧,确定1mol金属配合物吸收1molO2形成超氧配合物．     

新型噻吩基取代卟啉的合成及其荧光光谱研究

合成了两种新型噻吩基卟啉－5，15－二（2－噻吩基）－2，8，12，18－四乙基－3，7，13，17－四甲基卟啉7a（45．1％）和5，15－二（2－联噻吩基）－2，8，12，18－四乙基－3，7，13，17－四甲基卟啉7b(61.2%),并研究了它们的光谱性质，其中荧光光谱的最大发射峰蜂都在631nm处，量子产率分别为4．1％（7a)和1．4％（7b)。     

Multiple—Scattering of Near—Edge x—ray Absorption Fine Structure of Sulphur—Passivated InP（100） Surface

We use the multiple-scattering cluster method to calculated the sulphur 1s near-edge x-ray absorption fine structure (NEXAFS) of S-passivated InP(100) surface.The physical origins of the resonances in the NEXAFS have been unveiled.It is shown that the most important resonance is attributed to the photoelectron scattering between the central sulphur and the nearest indium atoms.The studies show that two S-S dimers with the bond lengths of 2.05A and 3.05A coexist in the surface,meanwhile the bridge and antibridge site adsorption of single S could not be ruled out.We support the scanning tunnelling microscopy result that the S-passivated InP(100) surface exhibits significant discorder.     

光照下meso-四(4-磺基苯基)卟啉(H_2TPPS)形成锌配合物的光-极谱研究

在氨性溶液中,光照射对ZnTPPS的形成影响很大。光-极谱试验表明:光电流(i_p)与浓度(c)间有以下的关系:对Zn(NH_3)_4~(2+),i_p∝C_((Zn)(NH_3)_4)~(2+)_~(1/2),对H_2TPPS,i_p∝C_(H_2TPPS),ZnTPPS络合物还原波的i_p不明显。本文对其差异性和光电流产生的原因做了初步探讨。     

A New Pathway to Synthesize Cyclomercurated Ferrocenylimines Containing Heterocyclic Ring

The cyclomercurated ferrocenylimines containing heterocyclic ring were prepared by the condensation of cyclomercuration of acylferrocene with the appropriate heterocyclic amine.This procedure provides an efficient method for the synthesis of cyclomerucurated ferrocenylimines containing heterocyclic ring which are difficultly synthesized by the conventional method.The reaction mechanism is proposed.     

金属卟啉催化条件下有机化合物与CO2的电羧化反应（Ⅴ）

研究了碘化四－（４－三甲胺基苯基）卟啉钴和ＶＢ１２催化ＣＯ２与卤代丁烷的电合成，该反庆在－１．５Ｖ（ｕｓ，ＳＣＥ）即可发生，ＶＢ１２催化产物为预期的戊酸丁酯，而ＣｏＴＰＰ催化产物为ＣＯ２直接还原的草酸二丁酯，并未发现ＣＯ２与卤代烷的反应产物，初步探讨了产生不同产物的原因。     

聚醚醚酮链结构与反应的模型化合物的量子化学研究

利用ＡＭ１方法对聚醚醚酮模型化合物全优化，结果为：芳环平均相互扭转角为３３．０度，桥键角１１７．０－１１８．０度，其分子结构拓扑图形表明：所有苯环（核）为平面构型，但其内角扭曲；其氢原子对苯环构型无实质性贡献，在更长链的计算中，冻结苯核与氢原子也得出满意结果，根据Ｍｕｌｌｉｋｅｎ键序与电荷讨论了醚交换与磺化反应。