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化学学报
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化学学报 ›› 2004, Vol. 62 ›› Issue (3): 225-229.    下一篇

研究通讯

芴衍生物的合成、结构与蓝色(λmax=418nm)双光子荧光

曹笃霞, 方奇, 薛刚, 许贵宝, 于文涛, 刘志强   

  1. 山东大学晶体材料国家重点实验室, 济南, 250100
  • 投稿日期:2003-08-07 修回日期:2003-12-15 发布日期:2014-01-26
  • 通讯作者: 方奇,E-mail:fangqi@icm.sdu.edu.cn E-mail:fangqi@icm.sdu.edu.cn
  • 基金资助:
    国家自然科学基金(No.20172034)和高等学校骨干教师资助计划项目.

Synthesis, Structure and Two-photon Excited Blue Fluorescence of Fluorene Derivatives

CAO Du-Xia, FANG Qi, XUE Gang, XU Gui-Bao, YU Wen-Tao, LIU Zhi-Qiang   

  1. State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100
  • Received:2003-08-07 Revised:2003-12-15 Published:2014-01-26

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分别以二苯胺和咔唑为端基,以芴为共轭桥, 合成了两个对称型芴衍生物:2,7-二-(N,N-二苯胺基)-9,9-二乙基芴[2,7-bis(N,N-diphenylamino)-9,9-diethyl-fluorene,简称DPDEF]和2,7-二咔唑基-9,9-二乙基芴(2,7-dicarbazol-9'-yl-9,9-diethyl-fluorene,简称DCDEF).用四圆X射线衍射方法测定了其晶体结构.DPDEF单晶属于单斜晶系,C2/c空间群.晶胞参数:a=2.8649(4) nm, b=0.85111(9) nm, c=2.7012(4) nm, β=100.982(11)º, V=6.4657(14) nm3, Z=8, Dc=1.144 g·cm-3, R=0.0581. DCDEF单晶属于单斜晶系,P21/c空间群.晶胞参数:a=0.92794(12) nm, b=0.88561(9) nm, c=3.7236(4) nm, β=96.914(9)º, V=3.0378(6) nm3, Z=4, Dc=1.208 g*cm-3, R=0.0652.晶体中DPDEF和DCDEF的芴桥具有很好的平面性,构成芴桥的两个苯环平面之间的夹角分别仅为3.0º和5.8º.在波长为730 nm的飞秒脉冲激光激发下,化合物DPDEF在THF中发出强的蓝色双光子上转换荧光(λmax=418 nm),测得双光子吸收截面为15 GM.

关键词: DPDEF, DCDEF, 芴衍生物, 蓝色上转换荧光

Two symmetrical fluorene derivatives with diphenylamino and carbazolyl as terminal group have been synthesized, which are named 2,7-bis(N,N-diphenylamino)-9,9-diethyl-fluorene (abbreviated to DPDEF) and 2,7-dicarbazol-9'-yl-9,9-diethyl-fluorene (abbreviated to DCDEF). Their crystal structures were determined by four-circle X-ray diffraction. DPDEF belongs to monoclinic system, C2/c space group, a=2.8649(4) nm, b=0.85111(9) nm, c=2.7012(4) nm, β=100.982(11)°, V=6.4657(14) nm3, Z=8, Dc=1.144 g·cm-3, R=0.0581. DCDEF belongs to monoclinic system, P21/c space group, a=0.92794(12) nm, b=0.88561(9) nm, c=3.7236(4) nm, β=96.914(9)°, V=3.0378(6) nm3, Z=4, Dc=1.208 g·cm-3, R=0.0652. The fluorene bridge shows perfect planarity with very small dihedral angle (3.0° for DPDEF and 5.8° for DCDEF respectively) between two involved phenyls. Pumped by 730 nm laser pulses, DPDEF exhibited strong blue up-converted fluorescence (λmax=418 nm) in THF with the two-photon absorption cross-section of 15 GM.

Key words: DPDEF, DCDEF, fluorene derivative, blue up-converted fluorescence