含咔唑樹狀化合物的合成與性質研究

Synthesis and Properties of New Carbazole- Containing Dendrimers

林育嫺(Yu-Hsien Lin)

指導教授 ： 汪根欉

國立臺灣大學/理學院/化學研究所/博士(2006年)

https://doi.org/10.6342/NTU.2006.02486

摘要

我們採用聯苯作為核心，成功地合成含1、2 、5和10 個咔唑作為樹枝化基元的啞鈴型樹狀化合物。這幾個樹狀化合物的放光在藍光區。另外一個合成的策略是利用1,8-萘二甲醯亞胺作為焦點，我們合成出了放出黃光樹狀化合物(29)及(30)。他們的螢光是來自於咔唑樹狀化合物進行能量轉移機制到1,8-萘二甲醯亞胺放光。接著我們以2-(9,9'-旋環雙芴)丙二腈作為焦點形成了樹狀化合物(35)及(36)。我們發現化合物(35)有電荷轉移的放光產生，而化合物(36)主要的放光則來自於區域性的激態。胺基化合物(10)與1,3,4-噁二唑樹狀化合物結合生成雙極性樹狀分子(42)及(43)會產生電荷轉移的放光。這些樹狀化合物都有很好的熱穩定性。經過多次循環伏安法的掃描來研究樹狀化合物聚合的發生，啞鈴型樹狀化合物及以1,8-萘二甲醯亞胺與2-(9,9'-旋環雙芴)丙二腈作為焦點的樹狀化合物會有聚合的現象，雙極性分子(42)及(43)則不會產生電聚合的現象。

關鍵字

樹狀化合物 ； 咔唑

並列摘要

We adopted biphenyl as a core, dendrimers containing with 1, 2, 5, and 10 carbazole groups as dendrons have been successfully synthesized. These dumbbelled shape dendrimers showed blue emission. In another strategy, using 1,8-naphthalimide as a focal point, we synthesized compounds 29 and 30 as yellow light emitting dendrimers. They showed efficient energy transfer from peripheral carbazole dendrons to the core. We used 2-(9,9'-spirobifluoren-2-ylmethylene)-malononitrile as a red emission focal point and synthesized compounds 35 and 36. We found compound 35 exhibited charge transfer fluorescence, but 36 showed the major emission from local excited state. Ambipolar dendrimers with amino compound 10 connecting to 1,3,4-oxadiazole dendrimer exhibited not only electron transfer but also energy transfer. These carbazole dendrimers exhibited good thermal stability. The electrochemical behavior of present carbazole-based dendrimers showed efficient electropolymerization, however, ambipolar dendrimers 42 and 43 didn’t undergo electropolymerization in CV studies.

並列關鍵字

dendrimer ； carbazole

參考文獻

40. (a) Zhang, Y.; Wada, T.; Sasabe, H. J. Mater. Chem. 1998, 8, 809. (b) Zhang, Y.; Wada, T.; Wang, L.; Sasabe, H. Chem. Mater. 1997, 9, 2798. (c) Zhang, Y.; Wang, L.; Wada, T.; Sasabe, H. Macromol. Chem.Phys. 1996, 197, 1877.

60. (a) Gilman, H.; Honeycutt, J. B. J. Org. Chem. 1956, 22, 226. (b) Thelakkat, M.; Schmitz, C.; Hohle, C. Strohriegl, P.; Schmidt, H.-W.; Hofmann, U.; Schloter, S.; Haarer, D. Phys. Chem. Chem. Phys. 1999, 1, 1693. (c) Gauthier, S.; Fréchet, J. M. J. Synthesis 1987, 383. (d) Lam, P. Y. S.; Vincent, G.; Bonne, D.; Clark, C. G. Tetradhedron Lett. 2003, 44, 4927 (e) Hameurlaine A.; Dehaen W. Tetradhedron Lett. 2003, 44, 957.

19. (a) Wiener, E. C.; Auteri, F. P.; Chen, J. W.; Brechbiel, M. W.; Gansow, O. A.; Schneider, D. S.; Belford, R. L.; Clarkson, R. B.; Lauterbur, P. C. J. Am. Chem. Soc. 1996, 118, 7774. (b) Bryant, L. H.; Brechbiel, M. W.; Wu, C.; Bulte, J. W. M.; Herynek, V.; Frank, J. A. J. Magn. Reson. Imaging 1999, 9, 348.

20. Thomas, T. P.; Patri, A. K.; Myc, A.; Myaing, M. T.; Ye, J. Y.; Norris, T. B.; Baker, J. R. Biomacromolecules 2004, 5, 2269.

5. (a) Tomalia, D. A.; Baker, H.; Dewald, J. R.; Hall, M.; Kallos, G.; Martin, S.; Roeck, J.; Ryder, J.; Smith, P. Polym. J. (Tokyo) 1985, 17, 117. (b) Tomalia, D. A.; Dewald, J. R.; Hall, M. J.; Martin, S. J.; Smith, P. B. Prepr. 1st SPSJ Int. Polym. Conf., Soc. Polym. Sci. Jpn. (Kyoto) 1984, 65.