高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (8): 1360.

• 论文 • 上一篇    下一篇

四溴-2,3-萘酞菁铅的合成及性质研究

贺春英1, 吴谊群1, 宋瑛林2, 王玉晓2, 左霞1   

  1. 1. 黑龙江大学化学化工学院, 哈尔滨150080;
    2. 哈尔滨工业大学物理系, 哈尔滨150001
  • 收稿日期:2002-09-11 出版日期:2003-08-24 发布日期:2003-08-24
  • 通讯作者: 吴谊群(1957年出生),女,博士,教授,从事配位化学研究.E-mail:yqwu8@hotmai.lcom E-mail:yqwu8@hotmai.lcom
  • 基金资助:

    国家自然科学基金(批准号:20141001);黑龙江省自然科学基金(批准号:B01-07)资助

Synthesis and Properties of Tetrabromo-2,3-naphthalocyanine Lead(Ⅱ)

HE Chun-Ying1, WU Yi-Qun1, SONG Ying-Lin2, WANG Yu-Xiao2, ZUO Xia1   

  1. 1. College of Chemistry and Chemical Technology, Heilongjiang University, Harbin 150080, China;
    2. Department of Physics, Harbin Institute of Technology, Harbin 150001, China
  • Received:2002-09-11 Online:2003-08-24 Published:2003-08-24

摘要: 以1,8-二氮杂双环[5.4.0]+-碳烯-7(DBU)为催化剂合成了中心原子为重原子铅、环取代基为重原子溴的萘酞菁配合物四溴-2,3-萘酞菁铅[PbNcBr4],并研究了该配合物的电子吸收光谱、热稳定性、光限幅特性及重原子对其光限幅特性的影响及其机理.该配合物在近红外区(795~825nm)有强吸收(Q带),溴取代可使配合物Q带略微蓝移,溶剂的极性对配合物的电子吸收光谱有较大影响.该配合物具有较高的热稳定性,气氛对其热稳定性有明显影响,其在N2气氛中的热稳定性明显比在O2气氛中的高;在O2气氛中为一步分解,在N2气氛中为多步分解.标题配合物具有优异的非线性光限幅特性,在高线性透射率88%时的限幅阈值为148mJ/cm2,限幅幅值为332mJ/cm2,损伤阈值约为3J/cm2,其光限幅特性明显优于光限幅新材料C60(透射率70%时,限幅阈值大于240mJ/cm2).重原子铅和溴可显著优化材料的非线性光限幅特性.

关键词: 四溴-2, 3-萘酞菁铅, 热稳定性, 光限幅特性

Abstract: Tetrabromo-2,3-naphthalocyanine lead(PbNcBr4) was synthesized in the presence of 1, 8-diazabicycloundec-7-ene(DBU) and its electronic absorption spectra, thermal stability, optical limiting property and the effect of bromine substituent on the above properties were investigated.There is one strong Q-absorption band in nearinfrared region.Bromine substituent attached to outer Nc ring results in the Q-band of PbNcBr4shifting to the blue compared to the complex unsubstituted.The polarity of solvents have influences on the electronic absorption spectra greatly< The complex shows high thermal stabilities and appears to be more stable in N2(the onset temperature 504.6 ℃) than in O2(the onset temperature 326.8 ℃).The thermal stabilities decrease on account of bromine substituent attached to outer Nc ring and declining extent changes with the varieties of atmosphere(decreased by 175℃ in N2, 25 ℃ in O2).Decomposition mechanisms differ according to the varieties of atmosphere with one step in O2and multi steps in N2.At a relatively high linear transmittance of 88%, the limiting threshold is 148mJ/cm2, the clamped fluence is 332 mJ/cm2, and the damage fluence is about 3J/cm2. The optical limiting behavior of PbNcBr4is better than that of C60whose limiting threshold is above 240 mJ/cm2with a linear transmittance of 70%. It can be regarded as a new kind of materials which has a better optical limiting property.

Key words: Tetrabromo-2,3-naphthalocyanine lead, Thermal stability, Optical limiting property

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