本論文設計並合成以吡嗪併咔唑、四取代噻吩、噻吩併吡嗪和喹喔啉結構單元為核心所構成不同共軛系統的模型分子，藉由各種系統的結構特性比較其雙光子吸收截面及其他的光學性質；論文中，也記錄了更具平面性外圍葉片的探路過程，這可以當作是未來銜接這方面計畫的重要參考文獻。非線性光學量測中，有利用飛秒雷射測其雙光子吸收所誘導螢光，並證實此螢光是由雙光子所誘導激發。以螢光比較法計算雙光子吸收截面以及利用奈秒雷射量測其光功率限幅及能量穩定性實驗並且利用此儀器測得三光子螢光，同時也證實是由三光子吸收所誘導激發，經由以上的光學數據得到以下的結論: [1] 在吡嗪併咔唑為核心的系統中是利用咔唑和芴兩結構單元以順向和反向對接的兩種異構物。反向的構型推測其分子內電荷轉移較好，因此有較佳的雙光子吸收表現。 [2] 四取代噻吩為核心的系統中，探討以噻吩延伸共軛鏈及將噻吩併為共平面中心兩者的性質，其中以噻吩延伸共軛鏈的結構會比噻吩併為共平面中心有較佳的雙光子吸收表現。 [3] 在噻吩併吡嗪和喹喔啉結構單元為核心的系統中，不同的共軛系統下其光學性質有明顯差異；將炔類作為共軛長度延伸，能讓雙光子吸收有很大的增幅。 ;Several conjugated systems with heterocyclic aromatic rings introduced as the π-centers including isomeric pyrazinoindenocarbazole, tetrathiophenyl benzene, anthratetrathiophene, thienopyrazine, and quinoxaline have been designed and synthesized to investigate their linear and nonlinear optical properties. Some useful structure-property relationships are revealed form our preliminary results: [1] For the pyrazinoindenocarbazole-cored chromophore system, the orientation of the fused heterocyclic rings plays an essential role to the molecular two-photon absorption strength. In our case, among the studied two isomeric structures, the one with anti- orm center exhibits superior two-photon absorptivity over the other one. [2] Thiophene could be a useful two-photon absorption promoting unit if it is correctly incorporated. It is found that the analogous dendritic structures with free and fused thiophene units as part of π-centers exhibit drastically different two-photon absorption strength. [3] In quinoxaline (benzopyrazine)- and thienopyrazine-cored system, it is found that thienopyrazine is an effective two-photon absorption band shifter. On the other hand, the substitution pattern in quinoxaline- cored chromophores play an important role to the molecular two-photon absorption, In addition, ethynyl unit is found to be an effective linkage to promote two-photon activity.
