摘要
在甲醇中三苄基氯化锡与3,4-二甲氧基苯甲酸发生脱烃基反应,合成了梯形四核有机锡氧簇合物[(μ-O)(μ-OMe)(L)Sn2(CH2Ph)4]2(HL=(MeO)2C6H3CO2H),经UV、IR、元素分析及X-射线单晶衍射表征结构。该晶体属三斜晶系,空间群P1,晶体学参数:a=1.225 6(5)nm,b=1.229 4(5)nm,c=1.378 0(5)nm,α=69.784(7)°,β=68.568(7)°,γ=72.926(7)°,V=1.780 1(12)nm3,Z=1,Dc=1.549 g·cm-3,μ(Mo Kα)=1.447 mm-1,F(000)=832,R1=0.0261,wR2=0.060 6。晶体结构分析表明:整个分子是以Sn2O2四元环为中心的对称结构,中心锡原子呈五配位畸变三角双锥构型。晶体中,两相邻的配合物分子经C-H…π作用组成一维带状结构。利用量子化学G03W软件,在LANL2DZ基组对配合物的稳定性、前沿分子轨道组成及能量进行研究。热重分析表明,配合物在128℃以下能稳定存在。此外,还研究了该配合物的荧光性质。
An organooxotin cluster [（U-O）U-OMe）（L）Sn2（CH2Ph）4]2 （HL=（MeO）2C6H3CO2H） has been synthesized by the dealkylation reaction of （PhCH2）3SnClwith 3,4-dimethoxybenzoic acid in methanol, and was characterized by UV, IR, elemental analysis and X-ray crystal diffraction. The crystal belongs to triclinic system, space group P1 with the cell parameters： a=1.225 6（5） nm, b =1.229 4（5） nm, c=1.378 0（5） nm, α=69.784（7）°, fl=68.568（7）°, y=72.926（7）°, V=1.7801（12） nm3, Z=I, Do=1.549 g.cm-3,/x（Mo Ko0=1.447 mm-1, F（000）=832, R1=0.026 1 and wR2=0.0606. Crystal structure shows a distorted trigonal bipyramidal configuration with five-coordination for the central tin atom, and the complex has a centrosymmetric structure mode with a four-membered central endocyclic Sn202 unit. Due to the C-H C...Л interactions between phenyl-H and benzene ring, the adjacent molecules of the complex is linked to generate ID ribbon structure. A theoretical investigation of one structural unit of the title complex was carried out using Gaussian03W at LANL2DZ level. The stability and the composition of the frontier molecular orbitals confirmed the coordination geometry of the crystal structure. Thermogravimetric analysis shows that the complex is stable up to 128 ℃. Moreover, its fluorescence spectra was also investigated. CCDC： 841414.
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
2014年第5期1135-1142,共8页
Chinese Journal of Inorganic Chemistry
基金
湖南省自然科学基金(No.13JJ3112)
湖南省科技计划(No.2013TZ2025)
湖南省高校创新平台开放基金(No.12K124)
教育厅一般项目(No.12C0537)
湖南省普通高校功能金属有机材料重点实验室开放基金(No.10K02)
衡阳市科技计划(No.2011KG56,2012KJ30)
衡阳师范学院青年骨干教师培养计划(2012)资助项目
关键词
有机锡氧簇合物
合成
晶体结构
量子化学
热稳定性
organooxotin cluster
synthesis
crystal structure
quantum chemistry
thermal stability
