非共平面芳香族發光體可藉由抑制分子內轉動(restricted intramolecular rotation, RIR)進而顯現聚集發光增強效應(aggregation-enhanced emission, AEE)。增強RIR現象之方式，除利用巨大基團限制分子轉動外，離子作用力亦為有效方法。本實驗利用長鏈離子材料提升RIR作用力，進而探討AEE發光性質。利用此長鏈作用力，將一微弱發光體十二烷基苯磺酸 (DBSA)與鹼性基團哌嗪(PZ) 與聚乙烯亞胺(PEI))於離子作用力下，觀察螢光發光之增強現象。另為印證長鏈作用力係提升AEE性質之論點，進一步將十二烷胺(DA)長鏈小分子與聯苯二磺酸鈉(BPS)、聚苯乙烯磺酸鈉）(PSS)，以離子作用力誘導形成規則性結構，使之展現AEE之發光特性。而在PSS(DA)1此離子系統內，觀察到出現出聚集增強激發二聚物發光(Aggregation enhanced excimer emission)之特殊現象。綜上，於DBSA(PZ)x、 DBSA(PEI)x、 BPS(DA)x 與PSS(DA)x等錯合物系統內，皆可利用長鏈自組裝行為，形成層狀超分子結構，故長鏈分子自組裝層狀結構與其發光行為係本研究之探討重點。

Restricted intramolecular rotation (RIR) of the non-coplanar aromatic fluorophores has been proven in several instances as the operative mechanism leading to the aggregation-enhanced emission (AEE) property. Besides using the bulky substituent as structural moiety of AEE-active materials, ionic bond interaction is also considered to be effective in reinforcing RIR. In this study, ionic ammonium sulfonate bond was used to introduce long chain orientation order and thus to impose effective RIR to generate emission enhancement on AEE-active organic fluorophores. With this aspect, a surfactant (surf) molecule of weakly-luminescent dodecylbenzenesulfonic acid (DBSA) was used to complex to different amines of varied structures and certain diamines (piperazine (PZ) and poly(ethyleneimine (PEI)) with right geometry to generate orientated dodecyl chains in the ionic products result in the further emission intensifications of the complex systems. Additionally, long-chain dodecylamine (DA) was used to react with weakly-fluorescent biphenyldisulfonate (BPS) and poly(styrene sulfonate) (PSS) to generate AEE-active materials with required orientation order and strong fluorescence due to the active RIR effect. An interesting aggregation-enhanced excimer emission (AEEE) was observed specifically for PSS(DA)1 complex system. Several complex systems (such as DBSA(PZ)x, DBSA(PEI)X, BPS(DA)x and PSS(DA)x ) were found to self-assemble into well-ordered supramolecular lamellar structures with the preferable orientation orders among their long aliphatic chains. RIR in relation to orientation order is therefore the main focus of this research.

Outline of Contents………………………………………………………….…………i
List of Figure................................................................................................................ iii
List of Scheme.............................................................................................................vii
List of Table............................................................................................................... viii
English Abstract........................................................................................................…ix
Chinese Abstract…………………………………………............................................ x
Chapter 1. Background................................................................................................1
1-1. Fluorescence and Phosphorescence…………………………………............1
1-2. Formation Mechanism of Excimer and Aggregation.....................................3
1-3. Aggregation Induced Emission Phenomenon(AIE).......................................6
1-4. Restriction of Intramolecular Rotation Response to Temperature.................8
1-5. Fluorescence Decay Dynamics......................................................................9
1-6. Aggregation-Enhanced Excimer Emission (AEEE).....................................11
1-7. Aggregation-Enhanced Emissions of Intramolecular Excimer Emission....12
Chapter 2. Experimental Sections............................................................................14
2-1. Materials.........................................................................................................14
2-2. Sample Preparation and Experimental Conditions.........................................18
2-3. Instrumentations..............................................................................................19
Chapter 3. Enhanced Luminescence by Restricted Intramolecular Rotation of Dodecylbenzenesulfonic Acid....................................................................................23
3-1. Introduction and Research Motivation............................................................23
3-2. Fluorescence of DBSA ...................................................................................26
3-3. Film Emission in Relationship to Linear/Heterocyclic Amines......................32
3-4. Enhanced Emission of DBSA by Complexation to PEI.................................39
3-5. The Dissociation of the Ionic Bond by Acidic TFA........................................44
3-6. Enhanced Thermal Stability by PEI Complexation…………........…………45
3-7. Relative Degree of Restricted MR on Pure DBSA and DBSA(PEI)x.............46
3-8. Time-Resolved Fluorescence Spectra.............................................................49
3-9. The Supramolecular Honeycomb Structure of DBSA(PEI)1.7 Complex........51
3-10. Conclusion....................................................................................................54
Chapter 4. Enhanced Emission by the Orientation Order of 1-dodecylamine.....55
4-1. Introduction and Research Motivation............................................................55
4-1-1. Intramolecular Excimer Formation of π-π Stacking....................................56
4-2. Fluorescence of Biphenyl Sulfonate (BPS) and Polystyrene Sulfonate
(PSS).................................................................................................................59
4-3. Fluorescence of BPS(DA)x and PSS(DA)x....................................................62
4-4. Orientation Order structure in Relation to the AEEE-Effect in Solid State....67
4-5. Time-Resolved Fluorescence Spectra.............................................................72
4-6. Conclusion......................................................................................................75
Chapter 5. Summary..................................................................................................76
References....................................................................................................................77
Supporting information................................................................................................86

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