中文摘要 本論文成功設計與合成出含四取代乙烯乙炔之染料分子與含類?喔?單元之多分岐染料分子，藉由延伸模型分子之π-電子共軛長度以增進其π-電子非定域化範圍，並改變模型分子連接之推/拉電子官能基集團、π- bridge結構及其分岐數以探討模型分子結構對雙光子吸收性質及其他光學性質之影響。由線性光學量測得知模型分子的最長吸收與最大發射波長、螢光量子產率，並以雷射激發光源得螢光生命期；透過飛秒時域雷射量測雙光子激發螢光與激發光源強度之關係證實此螢光經由雙光子吸收機制所產生、利用螢光比較法計算得到雙光子激發截面值。奈秒時域雷射則是測量模型分子在光學功率限幅行為上之表現、以及穩定脈衝雷射能量之作用。最後經由光學性質量測結果歸納以下結論： (1)延長分子共軛結構或於外圍增加推電子性官能基皆可有效提升雙光子激發截面，增進其非線性光學限幅表現；(2) 若於分子結構中導入類?喔?之拉電子性官能基，尤其是經延伸共軛長度之indenoquinoxaline結構，可促進分子內電荷轉移的程度，大幅提高模型分子的雙光子激發截面，且皆具有明顯的溶劑效應； (3) 若增加分子結構外圍的分支數目進而擴展成為多叉或樹狀型分子，其雙光子吸收效能將會大幅度提升。 Abstract This thesis aims to systematically design and synthesizie a number of model molecules with tetraethynylethene and quinoxalinoid structural units. We tentatively construct several model compounds with various structure. By changing their connecting electron-withdrawing group or electron-donating group , π-bridge and their number of branches, we can investigate how these changes in structure influence the two-photon absorptivities and other optical properties. After a series of linear and nonlinear optical measurements, our findings can be summarized as the following: The experimental results show that adding electron donor to the structure or extending the π-conjugation length will enhance the molecular two-photon absorptivities. We also found that inserting quinoxalinoid hetercyclic structures to our model chromophores especially indenoquinoxaline structure may exhibit strong two-photon activities and also cause outstanding solvent effects in solution phase.
