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Studies on Properties of Long Ladder Polysilanes with Double Helix Structures

双螺旋结构长梯形聚硅烷的性能研究

基本信息

批准号：
16550029
负责人：
KYUSIN Soichiro
金额：
$ 2.24万
依托单位：
Gunma University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

In this research project, long ladder polysilanes were synthesized, and their structures and properties were studied. Also, the dianion of the tricyclic ladder polysilane was isolated, and its structure and reactions were studied.The hexa- to octacyclic ladder polysilanes were synthesized by the coupling of 1,1,4,4-tetrachlorohexaisopropyl-tetrasilane and 1,1,2,2-tetrachlorodiisopropyldisilane with lithium. The X-ray analysis showed that the silicon skeletons of these compounds have double helix structures, and the twist angles between the terminal silicon-silicon rungs are 96.2 and 101.1°(hexacyclic), 119.6°(heptacyclic), and 128.5°(octacyclic). As the number of cyclotetrasilane rings of the ladder polysilanes increases, the lowest energy absorption maximum in the UV-visible spectra shifts bathochromically, and the oxidation potential decreases. Molecular orbital calculations showed that these electronic properties are explained by the destabilization of the energy level of the highest occupied molecular orbital (HOMO) and the stabilization of the energy level of the lowest unoccupied molecular orbital (LUMO).By the reduction of the tricyclic ladder polysilane with potassium in the presence of 18-crown-6, the silicon-silicon bond at the 1,2-positions of the tricyclic ladder polysilane was cleaved to give bis(2-potassiohexaisopropylcyclotetrasilanyl). The X-ray analysis showed that the inversion around the silicon atoms at the 1,2-positions took place during the reduction, and two potassium ions were incorporated into 18-crown-6. The reactions of this dianion with dimethyldichlorosilane or trimethylchlorosilane gave novel polysilanes with tricyclo[5.2.0.0^<2,5>]nonasilane and bis(cyclotetrasilanyl) skeletons.

本课题合成了长梯型聚硅烷，并对其结构和性能进行了研究。通过1，1，4，4-四氯六异丙基四硅烷和1，1，2，2-四氯二异丙基二硅烷与锂的偶联反应，合成了六至八环梯形聚硅烷。X射线衍射分析表明，这些化合物的硅骨架均为双螺旋结构，其末端硅-硅梯级间的扭转角分别为96.2 °和101.1°（六环）、119.6°（七环）和128.5°（八环）。随着梯形聚硅烷的环四硅烷环的数目增加，紫外-可见光谱中的最低能量吸收最大值向红色方向移动，并且氧化电位降低。分子轨道计算表明，这些电子性质是由最高占据分子轨道（HOMO）能级的不稳定和最低未占据分子轨道（LUMO）能级的稳定所解释的。将三环梯形聚硅烷的2-位裂解，得到双（2-六异丙基环四硅烷基钾）。X射线衍射分析表明，在还原过程中，在1，2-位的硅原子周围发生了反转，并且两个钾离子被引入到18-冠-6中。该二价阴离子与二甲基二氯硅烷或三甲基氯硅烷反应得到了具有三环[5.2.0.0 ^<2，5>]壬硅烷和双（环四硅烷基）骨架的新型聚硅烷。

项目成果

期刊论文数量（26）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

(trans-1,2,2,3,4,4-Hexa-tert-butyl-1,3-cyclotetrasilanediyl) dipotassium : Supramolecular Structure of the Silylpotassium-Benzene Complex

(反式-1,2,2,3,4,4-六叔丁基-1,3-环四硅烷二基)二钾：甲硅烷基钾-苯配合物的超分子结构

DOI：
发表时间：
2004
期刊：
Organometallics 23
影响因子：
0
作者：
S.Taniguchi;M.Minamoto;M.Matsushita;T.Sugawara;Y.Kawada;D.Bethel;Soichiro Kyushin
通讯作者：
Soichiro Kyushin

2,3,4,5-Tetrakis(dimethylsilyl) thiophene: The first 2,3,4,5-tetrasilylthiophene