摘要-1
本研究合成了兩種具有三臂及壓致變色性質之有機新穎發光材料tris(4-(4-phenylquinolin-2-yl)phenyl)amine (TPA-3Qu)和tris(4-(6-(9H-carbazol-9yl)-4-phenylquinolin-2-yl)phenyl)amine (TPA-3QuCz)。兩者皆具有特殊的壓力敏感性質，在壓力的作用下，皆會產生發光體放光波段發生改變之特殊性。不論是TPA-3QuCz或TPA-3Qu，其分子設計，皆是以具角錐狀構型(pyramidal)之三苯胺(triphenylamine)為分子中心。若中心延伸出去為較大的喹啉咔唑基團，即為TPA-3QuCz分子。TPA-3QuCz為一非結晶性物質，在微小的壓力作用下，即可產生高達112奈米的放光波段紅位移之現象。相反的，若是以三苯胺為中心延伸出去是較小的喹啉基團，即為TPA-3Qu分子。TPA-3Qu 為一結晶性物質，在巨大的壓力作用下(10 MPa)僅能產生相對較小的32奈米放光波段紅位移之現象。除了對壓力具有特殊敏感性外，TPA-3QuCz和TPA-3Qu也皆為熱致變色材料，在加熱的狀態下，兩者皆可產生與壓致變色相同成的放光紅位移現象。對於TPA-3QuCz 及TPA-3Qu 具有壓力及熱敏感性之性質，本文提出了分子構型平面化之模型解釋之。
摘要-2
此研究主題，合成了兩者新型態有機發光體，皆以四苯基噻吩 (TP) 為中心主幹，經由赫克反應 (Heck reaction)，接上了具有雙鍵的吡啶(pyridine)小基團和具有雙鍵的三苯胺(triphenylamine)大基團取代基，分別命名為TP-2Py 和 TP-2TPA。經由一系列光致放光測試，得知兩者皆具有聚集增益放光效應 (Aggregation Emission Enhancement effect)，比較TP-2Py 和 TP-2TPA 兩者的放光強度，發現無論在任何狀態的液態或固態下，TP-2TPA的放光效率(F)皆高於TP-2Py。借由變溫過程，探討液態狀況下TP-2Py 和TP-2TPA的放光性質，以及電腦模擬的輔助下，得知 TP-2TPA 相較於TP-2Py 具有較強的分子限制轉動能力。也因為具有較強的分子限制轉動，所以 TP-2TPA 可以抑制非放光型態的能量損失，進而擁有較好的放光效率。另一方面，我們也藉由混參 (blending) 聚乙烯醇 (polyvinyl alcohol) 於 TP-2Py 和 TP-2TPA 兩分子中，使得TP-2Py 和TP-2TPA 的含氮雜環，可與聚乙烯醇中的 -OH 官能基形成氫鍵，進而限制轉動，而有更進一步的增強發光效應。

Abstract - 1
Two tri-armed piezofluorochromic compounds of tris(4-(4-phenylquinolin-2-yl)phenyl)amine (TPA-3Qu) and tris(4-(6-(9H-carbazol-9yl)-4-phenylquinolin-2-yl)phenyl)amine (TPA-3QuCz) were prepared and found to exhibit keen fluorescence responses toward pressurization. With the framework of a twisted, pyramidal triphenylamine (TPA) center connecting to three large quinolinecarbazole (QuCz) arms, TPA-3QuCz is amorphous material exhibiting a large bathochromic shift of 112 nm under gentle grinding forces, which is in widely contrast to the small shift of 32 nm for TPA-3Qu when subjected to a high pressure load of 10 MPa. By heating to high temperatures, both TPA-3QuCz and TPA-3Qu also exhibited the same bathochromic shifts as pressurization did. Conformational transformations involving planarization of the arms were proposed to account for the observed fluorescence responses of TPA-3QuCz and TPA-3Qu towards pressure and heating.
Abstract -2
In this study, organic molecules of 4,4'-((1E,1'E)-((3,4-diphenylthiophene-2,5-diyl)bis(4,1-phenylene))bis(ethene-2,1-diyl))dipyridine (TP-2Py) with smaller substituent and 4,4'-((1E,1'E)-((3,4-diphenylthiophene-2,5-diyl)bis(4,1-phenylene))bis(ethene-2,1-diyl))bis(N,N-diphenylaniline) (TP-2TPA) with stronger substituent were prepared and characterized to identify
their photoluminescent (PL) responses toward the effect of aggregation emission enhancement (AEE). Comparing the fluorescence intensity for TP-2Py and TP-2TPA , no matter in the solid or solution state, the fluorescence of TP-2TPA is stronger than the TP-2Py. By the study influence of temperature on solution emissions of TP-2Py and TP-2TPA, and computer simulation, we realized the compound of TP-2TPA which could effective restriction on molecular rotation than the compound of TP-2Py. With the effector of effective restriction on molecular rotation, TP-2TPA can block the non-radiative energy loss, to enhance the efficiency of luminescence.
In another way, we also blends with hydroxyl-containing components (poly( vinyl alcohol) (PVA)) on both compounds,TP-2Py and tp-2TPA,. After blending with the hydroxyl components, the fluorescence can be further intensified due to the further restricted molecular rotation, though the facile intermolecular hydrogen-bond (H-bond) interactions between the nitrogen containing heterocyclic and the hydroxyl functions.

Abstract-1 (in Chinese).……………………………………………………………...i
Abstract-2 (in Chinese)………………………………………………………..ii
Abstract-1(in English)………………………………………………………………...iii
Abstract-2(in English)………………………………………………………………iv
Outline of Contents……………………………………………………………………v
List of Scheme……………….………………………………………..….………….vii
List of Figure…………………………………………………………………...........viii
List of Table……………...………………………………………….…………………x
Chapter 1 Highly-Sensitive Piezochromic Fluorophores with Tri-Armed Framework containing Triphenyl-Quinoline-Carbazole Moiety…………………………………...1
1-1 Introduction………………………………………………………………………..1
1-2 Experimental………………...................................................................................4
1-3 Results and discussion …………………………………………………………12
1-4 Conclusions………………………………………………………………………32
Chapter 2 Enhanced Emission by Restriction of Molecular Rotation
2-1.Introduction………………………………………………………………………33
2-2 Experimental.…………………………………………………………………….36
2-3 Results and Discussion.………………………………………………………….41
2-4 Conclusions…………………………………………….………………………60
Reference and Notes………………………………………………………………..61
Supporting Information……………………………………………………………..67

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