给-受体取代共轭多烯D—(CH＝CH)_n—A的NLO性质及协同推拉依赖性  

NLO Property and Synergy Push-pull Dependency of Donor/acceptor Substituted Conjugated Polyenes D—(CH＝CH)_n—A

作　　者：袁堂蜜 刘振波[1] 李雯[1] 李文佐[1] 程建波[1] Yuan Tangmi Liu Zhenbo Li Wen Li Wenzuo Cheng J ianbo(College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, Chin)

机构地区：[1]烟台大学化学化工学院,山东烟台264005

出　　处：《宁夏大学学报（自然科学版）》2017年第1期38-46,共9页Journal of Ningxia University(Natural Science Edition)

基　　金：山东省自然科学基金资助项目(ZR2013BM016);烟台大学大学生科技创新基金资助项目

摘　　要：研究多种推、拉电子基团端位取代H—(CH=CH)_n—H的电子结构,并在LC-BLYP/6-31G(d)水平上计算推电子基团(—NH_2,—OH,—NHCOH,—CH_3)、拉电子基团(—F,—Cl,—C_6H_5,—C≡CH,—CN,—CHO,—NO_2)对长程共轭烯烃分子结构的非线性光学性质的影响.结果表明,单独的推或拉电子基团均能有效地增大共轭多烯结构的超极化率(β0/a.u.).β0从结构H—(CH=CH)_6—H中的0.6分别增大到NH_2—(CH=CH)_6—H中的4.0×103和H—(CH=CH)_6—NO_2中的5.4×103;推、拉电子基团同时连接在共轭烯烃两端时,对β0存在协同作用.其中—NH_2与—NO_2的协同作用最明显,去除单纯—NH_2和单纯—NO_2取代对β0的贡献,协同作用的Δβ=4.6×10~3 a.u..β_0从结构H—(CH=CH)_6—H中的0.6.增大到NH_2—(CH=CH)_6—NO_2中的1.4×10~4,增大了大约2.3×104倍;结构NH_2—(CH=CH)_n—NO_2的β0随着链长n的增大而增大.提出一种推、拉电子基团协同作用提高共轭分子结构非线性光学性质的新策略.The article studies various types of push-pull electron group end position replacing electronic structure of —H（CH=CH）n—H,and calculates the influence of push electron donating group（—NH2,—OH,—NHCOH,—CH3） and pull electron donating group（—F,—Cl,—C6H5,—C ≡CH,—CN,—CHO,—NO2） on long-range conjugate alkene molecular structure＇s nonlinear optical properties in the level of LC-BLYP/6-31G（d）.The result shows that,either pure pushing or pulling the electron group can enlarge the hyperpolarizabilityβ0（a.u.）of conjugate alkene structure.β0enlarges from 0.6of H（CH=CH）6H structure to 4.0×10^3 of NH2—（CH=CH）6—H and5.4×10^3 of H（CH=CH）6—NO2 individually;puling and pushing electron group connecting both ends of conjugating alkene plays synergistic effect on the existence ofβ0,the synergistic role of —NH2and —NO2 is most obvious,apart from the attribution of pure —NH2and pure —NO2 replacement onβ0,the synergistic effectΔβ=4.6×103 a.u.β0enlarges from 0.6in structure of H—（CH=CH）6—H to 1.4 × 10^4 of NH2—（CH=CH）6—NO2,about 2.3 × 10^4 times;β0of structure NH2—（CH=CH）n—NO2 enlarges as the length of the extent of chain length.It raises a new strategy of push-pull electron group synergistic effect to enhance the molecular structure non-linear optical property.

关 键 词：给体 受体 第一超极化率 协同作用 

分 类 号：O641[理学—物理化学]