聚合硫化碳的稳定性和聚合活性  

Polymerizing activity and stability of carbonic sulfide polymers

作　　者：李平[1] 

机构地区：[1]四川大学化学学院,四川成都610064

出　　处：《化学研究与应用》2009年第3期293-302,共10页Chemical Research and Application

摘　　要：聚合硫化碳是集分子自组装、聚合硫化碳导体和半导体、非线性光学、化学活性中间体等多功能于一体的一类新型无机物。根据分子结构演变规律,在MPW1PW91/6-311G(d)水平上,设计CmSm+22-系列硫化碳分子的结构,计算其电子性质,得到了分子稳定化能与碳原子数之间所服从的线性关系,其中相关系数γ=0.9995,即每增加一个C2S2单元,稳定化能按线性关系ES=3/0.2214793/0.337059m降低,据此预测了部分聚合分子属稳定的聚合体。经原子轨道NBO布居数和共振结构计算分析,共轭π轨道的存在,是硫化碳聚合体稳定存在的原因,也是分子自组装、导电功能的结构基础。两端C2S2结构单元的化学活泼性和负电性预示,CmSm+22-硫化碳分子具有进一步聚合的活性,其独立负离子也易与各种基团结合形成稳定的化合物。Carbonic sulfide polymers are the newly inorganic compounds, which possess the functions of molecular self-assembly, semiconductors,non-linear optical and active chemical intermediates. A series of carbonic sulfide oligomers CmSm＋2^2-were at the MPW1PW 91/6-311G（d） level The stabilized energy versus the number of carbon atoms obeys the linear relation calculated statistically with the correlation coefficient y = 0.9995. The stabilized energies decease with increasing a C2S2 unit in terms of linear equation Es = - 0. 221479 - 0. 337059m. We found that the conjugative π orbitals stabilize the molecules and produce the functions of both molecular self-assembly and conductivity. The chemical activity at two terminal C2 S2 units indicates that the carbonic sulfide oligomers possess the capability of polymerization. The isolated anions react easily with various radicals to generate the stable compounds.

关 键 词：聚合硫化碳 线性关系 共轭效应 稳定化能 电子结构 

分 类 号：O641.121[理学—物理化学]