有机化学 ›› 2015, Vol. 35 ›› Issue (2): 432-438.DOI: 10.6023/cjoc201409003 上一篇    下一篇

研究论文

萤火虫氨基氧化荧光素相似物作为有机发光二极管材料的理论研究

闵春刚a, 李作盛b, 崔小英a, 杨喜昆a, 黄绍军a, 王绍华a, 任爱民b   

  1. a 昆明理工大学分析测试研究中心 昆明 650093;
    b 吉林大学理论化学研究所 理论化学计算国家重点实验室 长春 130023
  • 收稿日期:2014-09-03 修回日期:2014-10-13 出版日期:2015-02-25 发布日期:2014-10-21
  • 通讯作者: 闵春刚, 任爱民 E-mail:minchungang@163.com;aimin_ren@yahoo.com
  • 基金资助:

    国家自然科学基金(Nos. 21473071, 21173099, 21363012, 51363012, 51374117)、国家重点基础研究发展规划(973计划, No. 2013CB834801)、高校基础科学研究专项、云南省应用基础研究计划(No. 2011FZ040)、云南省教育厅科学研究基金(No. 2012Y545)、昆明理工大学人才培养基金(No. KKSY201232040)和吉林大学理论化学计算国家重点实验室开放课题基金资助项目.

Theoretical Investigation on Firefly Oxyluciferin Analogs Bearing an Amino Group Used as Organic Light-Emitting Diodes Materials

Min Chunganga, Li Zuoshengb, Cui Xiaoyinga, Yang Xikuna, Huang Shaojuna, Wang Shaohuaa, Ren Aiminb   

  1. a Research Center for Analysis and Measurement, Kunming University of Science and Technology, Kunming 650093;
    b State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023
  • Received:2014-09-03 Revised:2014-10-13 Online:2015-02-25 Published:2014-10-21
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21473071, 21173099, 21363012, 51363012, 51374117), the National Key Basic Research Program (973 Program, No. 2013CB834801), the Special Funding to Basic Scientific Research Projects for Central Colleges, the Applied Basic Research Plans Program of Yunnan Province (No. 2011FZ040), the Scientific Research Fund of Yunnan Provincial Education Department (No. 2012Y545), the Training Foundation for Talents of Kunming University of Science and Technology (No. KKSY201232040) and the Foundation of State Key Laboratory of Theoretical and Computational Chemistry.

由于萤火虫荧光素具有发光效率高, 能发出从绿色到红色多种颜色光的特点使其在有机发光器件领域存在巨大的应用潜力. 为了探索结构和性质的关系, 我们用苯并吡喃、联苯、联吡啶、菲、邻二氮杂菲、芴和晕苯取代氧化荧光素中的苯并噻唑部分, 设计了一系列氨基氧化荧光素相似物. 本工作用密度泛函理论和含时密度泛函理论方法对这些化合物进行了一系列光电性质的研究. 计算结果表明, 含有氮原子的氨基联吡啶氧化荧光素(BPAOL)和氨基邻二氮杂菲氧化荧光素(PMAOL)与含有碳原子的氨基联苯氧化荧光素(BIAOL)和氨基菲氧化荧光素(PHAOL)比较具有较小的最高占据分子轨道(HOMO)和最低非占据分子轨道(LUMO)轨道能量及更大的电离能(IP)和电子亲和势(EA)值. 化合物氨基氧化荧光素(AOL), BIAOL, BPAOL, PHAOL, PMAOL, 氨基芴氧化荧光素(FLAOL)和氨基晕苯氧化荧光素(COAOL)可以作为电子注入/传输材料. AOL、PHAOL、FLAOL和COAOL可以作为蓝色发光材料.

关键词: 电离能和电子亲和势, 重组能, 氧化荧光素相似物, 发射光谱, 含时密度泛函理论

Firefly oxyluciferin has great potential application in organic light-emitting devices, because of the high efficiency and wide range of multicolor light from green to red. To gain an insight into the structure-property relationships, a set of firefly oxyluciferin analogs bearing an amino group with benzopyran, biphenyl, bipyridine, phenanthrene, phenanthroline, fluorine and coronene instead of benzothiazole ring were designed. In this study, a systematic investigation into them was carried out using the density functional theory and time-dependent density functional theory methods. The calculated values show that bipyridylaminooxyluciferin (BPAOL) and orthophenanthrolylaminooxyluciferin (PMAOL) with nitrogen atom have smaller the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energies, larger ionization potential (IP) and electron affinity (EA) values than biphenylaminooxyluciferin (BIAOL) and phenanthrylaminooxyluciferin (PHAOL) with carbon atom. Compound aminooxyluciferin (AOL), BIAOL, BPAOL, PHAOL, PMAOL, fluorenylaminooxyluciferin (FLAOL) and coronenylaminooxyluciferin (COAOL) can be used as electron-injection/transporting materials. AOL, PHAOL, FLAOL and COAOL can be used as blue light-emitting materials. These results indicate that the firefly oxyluciferin analogs bearing an amino group have many interesting properties and are good candidates for optoelectronic ap-plication.

Key words: ionization potential and electron affinity, reorganization energy, oxyluciferin analogs, emission spectrum, time-dependent density functional theory