N치환체를 갖는 Diphenylmaleimide계 형광유기고분자의 합성 및 그의 치환체 변화에 따른 형광특성에 관한 연구 = Study on thd synthesis of organic fluorescent polymers having N-substituted1,2-diphenyleimide moieties and thd differences of florescent properties with N-substituents

다국어 초록 (Multilingual Abstract)

Organic fluorescent materials in field of LASER, LEDs (Light Emitting Diodes), optical amplifiers and biosensors, are the most spotlighting materials. In these days, a point of the study is development of materials having excellent luminescent efficiency, thermal stability, and various functionalities, etc. In our laboratory, a -conjugated polymer having an organic fluorescent moiety, a N-substituted 1,2-diphenylmaleimide structure, was reported. The polymer showed excellent luminescent efficiency and thermal stability. In this study, model compounds and polymers having a N-substitued 1,2-diphenylmaleimide moiety were synthesized. As the structure of a N-substituent was bulkier, or the electron density of a N-substituent was denser, the photoluminescence intensity was higher. All the compounds showed greenish yellow photoluminescence with the maxima between 510 and 537 nm. The polymers showed high solubility in common organic solvents.

국문 초록 (Abstract)

유기형광색소는 레이저, 발광 다이오드, 광증폭기, 등의 전기광학 및 광학소자와 화학, 바이오 센서 등의 첨단 응용분야에서 크게 각광 받고있는 소재로서 이에 대한 학술적, 공업적 응용에 대한 연구가 활발히 진행되고 있다. 최근에는 발광효율 및 색상조절과 색순도가 우수하고 내열성과 광산화 안정성이 우수하면서 다양한 기능성을 가진 형광재료 개발에 연구의 초점이 맞추어지고 있다. 본 연구실에서는 최근 N치환된 1,2-diphenylmaleimide구조의 형광색소를 기본 단량체로 하는 공액고분자를 발표한 바 있다. 본 연구에서는 N치환된 1,2-diphenylmaleimide구조를 가지는 유기형광색소를 N치환체를 바꿔가면서 합성하였고, 치환체의 특성에 따른 형광특성을 알아보았다. 예상대로 N치환체가 측쇄를 많이 가져서 부피가 클수록, 즉, 입체장애가 클수록, 또는 치환체의 전자밀도가 클수록 형광현상은 크게 관찰되었다. 또한 고분자로 합성하였을 때에도 그러한 성질을 그대로 유지했다.

목차 (Table of Contents)

• 1. Introduction ----------------------------------------------------------1
• 2. Background ----------------------------------------------------------3
• 2-1. Luminescence in the solid polymers --------------------------------3
• 2-2. Energy transfer in the solid state ------------------------------------4
• 2-2-1. Singlet states------------------------------------------------------4
• 2-2-2. Triplet states ------------------------------------------------------7
• 3. Experimental --------------------------------------------------------------10
• 3-1. Materials -------------------------------------------------------------10
• 3-2. Synthesis of model compounds ------------------------------------10
• 3-2-1. 3,4-Bisphenyl-3-cyclobutene-1,2-dione(1) ------------10
• 3-2-2. 3,4-Bisphenyl-2,5-furanedione (2) -----------------------11
• 3-2-3. 3,4-Bisphenyl-N-phenyl-pyrrole-2,5-dione (3) -------------12
• 3-2-4. 3,4-Bisphenyl-N-2- methyl-phenyl-pyrrole-2,5-dione
• (4) -----------------------------------------------------------12
• 3-2-5. 3,4-Bisphenyl-N-2, 6-dimethyl-phenyl-pyrrole-2,5-
• dione (5) ----------------------------------------------------13
• 3-2-6. 3,4-Bisphenyl-N-2,6-diisopropyl-phenyl-pyrrole-2,5-
• dione (6) ------------------------------------------------13
• 3-2-7. 3,4-Bisphenyl-N-4-nitrophenyl-pyrrole-2,5-dione (7)
• --------------------------------------------------------------------14
• 3-2-8. 3,4-Bisphenyl-N-4-pyridyl-pyrrole-2,5-dione (8) ---14
• 3-2-9. 3,4-Bisphenyl-N-pentafluorophenyl-pyrrole-2,5-dione
• (9) ---------------------------------------------------------------15
• 3-3. Synthesis of polymers---------------------------------------------15
• 3-3-1. 3,4-Bis(4-bromophenyl)-N-phenyl-pyrrole-2,5-dione
• (10), 3,4- Bis(4- bromophenyl)- N-2,6- isopropylphenyl-pyrrole-2,5-dione (11) ------------------------15
• 3-3-2. Poly(3,4-bisphenyl-N-phenyl-pyrrole-2,5-dione) (12)
• --------------------------------------------------------------16
• 3-3-3. Poly(3,4-bisphenyl-N-2,6-diisopropyl-phenyl-pyrrole-
• 2,5-dione) (13) -----------------------------------------------17
• 3-4. Measurements-----------------------------------------------------17
• 4. Results and Discussion--------------------------------------------19
• 4-1. Model compounds synthesis and characteristics-----------19
• 4-1-1. 3,4-Bisphenyl-2,5-furanedione ---------------------------19
• 4-1-2. Synthesis of 1,2-diphenylmaleimides -----------------------23
• 4-2. Polymers synthesis and characteristics ----------------------33
• 4-3. Optical characteristics-------------------------------------------40
• 5. Conclusions---------------------------------------------------------46
• 6. References-----------------------------------------------------------47