合成含呋喃與菲之環芃烯

環芃這類化合物對於研究放光團透過空間作用是個好的模型。雜環環芃烯也是令人感興趣的系統，但文獻中含呋喃環芃烯是較少被關注的。而菲這個類平面芳香環，在環芃烯系統中其易聚集的性質，在光物理上已廣泛的被討論。　　過去我們已成功地利用呋喃成環反應，與McMurry反應合成到一系列的含呋喃之[n.2]環芃烯40a-f與環芃雙烯67。並經由EFISH，HRS的實驗確定這類化合物具有非線性光學性質。而為了深入了解這類系統，我們引入菲於環芃烯中，合成到環芃雙烯類似物69與70，兩者由EFISH實驗確定都有μβ值。也讓我們知道，將67中二苯代乙烯的架構，置換成菲結構的69或70，導致原雙鍵可當作acceptor的性質，在換成菲後變得不明顯。且由核磁共振光譜的動力學實驗與DFT理論計算，可知菲提供了69與70更加剛性的構型，導致另ㄧ端雙鍵部份，形成具有強環張力性質的雙鍵，是導致69有非線性光學性質的主因之一。但不同的是，在70中呋喃當donor而強拉電子基乙基酯當acceptor可形成電荷分離的結構，因而具有非線性光學性質。而正丁基呋喃環芃烯40a，67，69並不具有強推拉電子基，但構型上存在著具有環張力性質的雙鍵，可當acceptor與呋喃當donor的性質共同發揮，使其具有非線性光學特性。

關鍵字

呋喃；菲；環芃烯；非線性光學

並列摘要

Cyclophanes have provided useful models for the investigation of through-space interactions between chromophores. Heterophanes also were interesting systems, but the discussing of furan-containing cyclophene was rare. It was well documented that phenanthrene-containing cyclophene, such a ring and planar aromatic structure was easy aggregated in photophysic. 　　Recently, we have detailed a new series of furan-containing teraryl cyclophene derivatives 40a-f and 67. And two keys to syntheses were one-pot furan annulation and the McMurry reaction. It is noteworthy that they exhibit unusually large Stokes shifts and NLO properties through EFISH or HRS experiment. In order to going deeper to these cyclophenes, we obtained furan, phenanthrene-containing cyclophenes 69 and 70 which exhibit NLO properties and μβ value. 　　It’s different property that a double bond as an electron acceptor, when cis-stilbene of 67 was replaced to phenanthrene of 69 or 70. And 69 contained the high rigid structure and a strong twisted double bond, which were proved by dynamic NMR experiment and DFT calculation. Such a twisted system may thus induce significant enhancement in hyperpolarizability. It’s interesting to note that 70, contained the strong electron withdrawing group (-CO2Et), was different property that charge transfer could only occur in the furan moiety with ester group from others. We expected a bridged double bond as an electron acceptor and furan as an electron donor for optical nonlinearity of cyclophenes may only take place in n-Bu substituted cases (40a, 67 and 69).

並列關鍵字

Furan ； Phenanthrene ； Cyclophenes ； NLO

參考文獻

[1] Pellegrin, M. Rec. Trav. Chim. Pays. Bas. 1899, 18, 558.

[4] Sekine, Y.; Brown, M.; Boekelheide, V. J. Am. Chem. Soc., 1979, 101, 3126.

[11] (a) Woo, H. Y.; Hong, J. W.; Liu, B.; Mikhailovsky, A.; Korystov, D.; Bazan, G. C. J. Am. Chem. Soc. 2005, 127, 820; (b) Woo, H. Y.; Korystov, D.; Mikhailovsky, A.; Nguyen, T.-Q.; Bazan, G. C. J. Am. Chem. Soc. 2005, 127, 13794; (c) Bartholomew, G. P.; Rumi, M.; Pond, S. J. K.; Perry, J. W.; Tretiak, S.; Bazan, G. C. J. Am. Chem. Soc. 2004, 126, 11529.

[14] Cram, D. J.; Allinger, N. L.; Steinberg, H. J. Am. Chem. Soc. 1954, 76, 6132.

[16] (a) Azumi, T.; McGlynn, S. P. J. Chem. Phys. 1964, 41, 3131.

國際替代計量

合成含呋喃與菲之環芃烯

全文下載

主題瀏覽