Luận án: Tổng hợp & đặc trưng polyme liên hợp làm cảm biến huỳnh quang - Bùi Thanh Thảo

aSOÁo sas B03 ; VIETNAM NATIONAL UNIVERSITY — HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY BUI THANH THAO SYNTHESIS AND CHARACTERIZATION OF CONJUGATED POLYMERS ORIENTED FOR FLUORESCENCE CHEMOSENSOR DOCTOR OF PHILOSOPHY THESIS IN CHEMICAL ENGINEERING : HO CHI MINH CITY - 2023 8 SOO Sree 22 $]0 3 VIETNAM NATIONAL UNIVERSITY — HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY BUI THANH THAO SYNTHESIS AND CHARACTERIZATION OF CONJUGATED POLYMERS ORIENTED FOR FLUORESCENCE CHEMOSENSOR Major: Chemical Engineering Major code: 62520301 Independent examiner: Independent examiner: Examiner: Assoc. Nguyen Anh Tien Examiner: Prof. Phan Bach Thang Examiner: Assoc. Ha Thuc Chi Nhan Advisor: Assoc.

Nguyen Tran Ha il DECLARATION OF ORIGINALITY Thereby declare that this is my own research study. The research results and conclusions in this thesis are true, and are not copied from any other resources. The literature references have been quoted with clear citation as requested. Thesis Author Bui Thanh Thao 11 ABSTRACT A conjugated diblock copolymer of poly(3-hexylthiophene)-block-poly(2-(4,6- dichlorotriazin-2-yl]oxy)ethyl methacrylate) (P3HT-b-PDCTMA) has been obtained via the combination of Grignard metathesis method (GRIM) and organo-catalyzed atom transfer radical polymerization reaction (ATRP) with a polymerization conversion of 73%.

The synthesized diblock copolymer P3HT-b-PDCTMA exhibited an Mn of 17,500 g/mol, which is approximately close to the theoretical value, and with a polydispersity index (PDI) of 1. The conjugated diblock copolymer P3HT-b-PDCTMA bears functional reactive triazine chloride groups that act as a platform to react with mercaptan or amine groups via efficient nucleophilic aromatic substitution reactions. In addition, diblock copolymers based on the rod segment of regioregular poly(3- hexylthiophene) (P3HT) and a coil segment of poly(2-(dimethylamino)ethyl methacrylate-random-1-pyrenylmethyl methacrylate) (PEDMAEMA-r-PyMA)) was also synthesized successfully by Grignard metathesis method and atom transfer radical polymerization reaction. The obtained copolymer was well-defined with an average molecular weight of 11,300 g/mol and low polydispersity below 1.

Interestingly, P3HT-b-P(DMAEMA-r-PyMA) was examined as a possible chemosensor for trace detection of the trinitrotoluene (TNT) explosive. On the other hand, the conjugated molecules based on pyrene and dithienopyrrole derivatives including 4-(2-ethylhexyl)-2-(pyren-1-yl)-4H-dithieno[3,2-b:2’,3’- d]pyrrole (EP4HP) and 4-(2-ethylhexyl)-2,6-di(pyren-1-yl)-4H-dithieno[3,2-b:2’,3’- d]pyrrole (EDP4HP) have been successfully synthesized via C—H direct arylation reaction. The conjugated molecules exhibited efficient fluorescence quenching toward herbicide mesotrione as nitroaromatic pesticides that could be promising candidates as the chemosensor for tracing nitroaromatic pesticides. Finally, two novel low-bandgap conjugated donor-acceptor copolymers poly(alkyl-POZ-DPP) and poly(benzoylalkyl-POZ-DPP) based on phenoxazine with ethylhexyl/hexyl benzoyl side chain and diketopyrrolopyrrole were successfully synthesized by Pd-catalyzed direct arylation coupling polycondensation.

The iV phenoxazine-based polymers with hexyl benzoyl side chains have higher molecular weights than those with branched ethylhexyl side chains and the benzoyl substitution also resulted in a broadening and redshift of the solid-state absorption spectra of the corresponding copolymer. TÓM TAT Luận án nay mô tả các nghiên cứu liên quan đến tổng hợp và các đặc tính của các diblock polyme liên hợp trên cơ sở poly(3-hexylthiophene) định hướng ứng dụng làm vật liệu cảm biến huỳnh quang phát hiện hợp chất nỗ TNT. Ngoài ra, nghiên cứu nay còn nhằm mục đích tổng hợp các polyme liên hợp và các phân tử nhỏ có cấu trúc cho nhận điện tử dùng dé nhận biết mesotrione, một trong những hợp chất độc hại nhất được sử dung trong thuốc trừ sâu. Chương đầu tiên của luận án này cung cấp tông quan tài liệu về các polyme liên hợp.

Luận án này đưa ra các nghiên cứu về diblock copolyme dựa trên poly(3- hexylthiophene) và con đường dé tổng hợp các polyme liên hợp. Chương thứ hai trình bày chỉ tiết tất cả các thí nghiệm trong đó các hóa chất và dụng cụ để mô tả đặc tính của polyme liên hợp. Các polyme liên hợp này được đặc trưng thông qua Quang phô hồng ngoại (FT-IR), Quang phô cộng hưởng từ hạt nhân (1H NMR và '3C NMR), Phân tích nhiệt trong lượng (TGA), Phân tích nhiệt quét vi sai (DSC), Quang phố hap thụ phân tử (UV- Vis), Quang phô huỳnh quang, Kính hién vi lực nguyên tử (AFM), Sắc ký thâm thấu gel (GPC). Chương thứ ba của luận án này mô tả cấu trúc và tính chất của polyme liên hợp thu được bao gồm cấu trúc hóa học, tính chất quang và nhiệt.

Ngoài ra, mối quan hệ giữa cấu trúc hóa học và tính chất quang học của polyme liên hợp đã được nghiên cứu về cau tạo của chúng. Việc ứng dụng các polyme liên hợp để nhận biết các hợp chất nỗ TNT và mesotrione cũng được thực hiện và thảo luận trong chương này. Chương cuối trình bày kết luận và kiến nghị. Theo hiểu biết tốt nhất của chúng tôi, các polyme liên hợp này chỉ được nhóm nghiên cứu của chúng tôi công bé và chưa được đề cập trong các nghiên cứu trước đây.

VI ACKNOWLEDGMENT I reserve special thanks to my research advisor, Assoc. Nguyen Tran Ha, who have supported me over the course of my research work. Their motivation, patience, enthusiasm, and immense knowledge have kept me going during the past four years. I was so lucky to have such a precious opportunity to work under their guidance.

I really would like to learn more from such renowned and respected chemists. I would also like to thank Prof. Phan Thanh Son Nam for their insight and questions that have undoubtedly helped me progress to this point, guiding me on how to recognize and find the best ways to solve scientific problems. I would be remiss if I did not acknowledge all members of my group (Doan Kim Bao, Nguyen Huu Tam, Tran Duc Chau) for the stimulating discussions in Chemistry Division.

Additionally, I wish to acknowledge four undergraduate students (Nguyen Thi Cam Hong,) and a graduate student (Nguyen Le Phuong Thao) for their help during the time they studied in the laboratory. I would like to express my sincere gratitude to Mr. Nguyen Cong Mau for always encouraging me whenever I step back or face difficulties in studying. I would like to thank my best friend: Assoc.

Dang Huynh Giao who has always been by my side encouraging, reminding and accompanying me throughout my study. I would also like to thank the Leader: Assoc. Pham Van Phuc and my colleagues: MS. Doan Thi Bich Loc and MS.

Nguyen Thi Xuan Trang at the Science and Technology Development Journal, VNU-HCM for encouraging me, creating favorable conditions, and supporting me so that I could complete the project. My deepest gratitude to my family: my parents, my husband Duong Vinh Hung and my daughter Nguyen Ngoc Xuan Mai. The support and love from my family is of inestimable value. Vil TABLE OF CONTENTS 1 )ý.

vii TABLE OF CONTENTS. 3 2 HH HH TH HT nu TH Hàng Vili I&JM9)303/600. xii LIST OF SCHEMES.- - LH 9T HH HH HH HH XV IR09)s00. XVI LIST OF ABBREVIA TION.- Sàn HH HH HH TH HH TH Hệ XVII J§ §›{6)9)0/@19))aẢ44::.

1 CHAPTER 1 LITERATURE REVIEW.1 Structure of Conjugated Polymer and Mechanism of Conduction .2 Application of Conjugated POÏyIT€T. nh ng nh 6 1.2 Polymeric Solar Cells (PSCS).3 Organic Field-Effect Transistor (OFE”T}).4 The evolution of polythiophenes .5 Synthesis of regioregular poly(3-alkylthiophenes) (rr-P3ATs) .6 Mechanism of the nickel-catalyzed polymer1zafIon.8 Control end group of P3HT and block copolymers containing P3HT.3 Controlled radical polymerization (CRP). -- Ăn HH ng HH HH, 22 1.2 Atom Transfer radical polymerization (ATRP) .4 Conjugated polymer for fluorescence sensory appÌICation.5 Research works in the field by foreign scientists and Vietnamese scientists.6 Aims and ObJ€C[IV€S oo. ee cece 5E 11v TH HH 30 CHAPTER 2.- --- 5 5 kg ng gi, 32 PP oi).1 Synthesis of 2-bromo-3-hexylthiophene (compound 2, scheme 3.2 Synthesis of 2-bromo-3-hexyl-5-iodothiophene (compound 3, scheme 3.3 Synthesis of 2-([4,6-dichlorotriazin-2-yl]oxy)ethyl methacrylate (DCTMA) (compound 8, scheme 3.4 Synthesis of 1-pyrenylmethyl methacrylate (PyMA) (compound 8, scheme 2 .5 Synthesis of 4-(2-ethylhexyl)-4h-dithieno[3,2-b:2',3'-d]pyrrole (EDP) (compound 1, scheme 66020007077.6 Synthesis of 1-Bromopyrene (compound 2, scheme 3.7 Synthesis of 4-(2-ethylhexyl)-2-(pyren-1-yl)-4h-dithieno[3,2-b:2',3'- d]pyrole (EP4HP) and 4-(2-ethylhexyl)-2,6-di(pyren-1-yl)-4h-dithieno[3,2- b:2',3'-d]pyrrole (EDP4HP) (scheme 3.8 Synthesis of monomer 10-(2-ethylhexyl)-10H-phenoxazine (compound M1, SCHEME in.9 Synthesis of monomer 10-(4-(hexyl)benzoyl)-10H-phenoxazine (compound M2, Scheme 3.4 Synthesis of conjugated diblock copolymers based on poly(3-hexylthiophene) 40 2.1 Synthesis of regioregular head-to-tail poly(3-hexylthiophene) with H/Br end group (compound 4, scheme 3.

-- -- << E411 91 1E TH ng ng tiệt 40 2.2 Synthesis of regioregular head-to-tail poly(3-hexylthiophene) with CHO/Br end group (compound 5, scheme 3.3 Synthesis of regioregular head-to-tail poly(3-hexylthiophene) with CH2OH/Br end group (compound 6, scheme 3.4 Synthesis of bromoester-terminated poly(3-hexylthiophene) (compound 7, 9i 0100 ad.5 Synthesis of poly(3-hexylthiophene)-block-poly(2-([4,6-dichlorotriazin-2- yl]oxy)ethyl methacrylate) (P3HT-b-PDCTMA) diblock copolymers (compound P1,. ----::-:-:AÖÖÖÔố ca ae 41 1X 2.6 Functionalization reaction of poly(3-hexylthiophene)-block-poly(2-([4,6- dichlorotriazin-2-yl]oxy)ethyl methacrylate) (P3HT-b-PDCTMA) _ diblock copolymer with furfuryl mercaptan (compound P2, scheme 3.7 Functionalization reaction of poly(3-hexylthiophene)-block-poly(2-([4,6- dichlorotriazin-2-yl]oxy)ethyl methacrylate) (P3HT-b-PDCTMA) | diblock copolymers with benzyl mercaptan (compound P3, scheme 3.8 Functionalization reaction of poly(3-hexylthiophene)-block-poly(2-([4,6- dichlorotriazin-2-yl]oxy)ethyl methacrylate) (P3HT-b-PDCTMA) _ diblock copolymer with furfurylamine (compound P4, scheme 3.9 Functionalization reaction of poly(3-hexylthiophene)-block-poly(2-([4,6- dichlorotriazin-2-yl]oxy)ethyl methacrylate) (P3HT-b-PDCTMA) _ diblock copolymers with benzylamine (compound P5, scheme 3.10 Synthesis of Poly(3-hexylthiophene)-b-poly(2-(dimethylamino)ethyl methacrylate-random-1-pyrenylmethyl methacrylate) (P3HT-b-P(DMAEA-r- PyMA)) (compound 9, scheme 3.5 Synthesis of donor-acceptor conjugated copolymers poly(alkyl-POZ-DPP) and poly(benzoylalkyl-POZ-DPP) via direct arylation polycondensation (compound P1 and P2, scheme 3.ccccsccccccessssscccceesesscececesessseeeceeesssseeeccesessseeececeessaeeeceeeeesteeeeeeees 45 CHAPTER 3 RESULT AND DISCUSSION.1 Synthesis of conjugated diblock copolymers Poly(3-hexylthiophene)-b-poly(2- ([4,6-dichlorotriazin-2-yl]oxy)ethyl methacrylate) (P3HT-b-PDCTMA).1 Synthesis and characterization of Poly(3-hexylthiophene)-b-poly(2-([4,6- dichlorotriazin-2-yl]oxy)ethyl methacrylate) (P3HT-b-PDCTMA).2 Funtionalization of diblock copolymer P3HT-b-PDCTMA (P1-P5) via thiol- triazine and amine-triazine substitution T©aCfIOTS.3 Solvent induced aggregation of diblock copolymers P1-P5 .2 Synthesis of conjugated diblock polymer poly(3-hexylthiophene)-block-poly(2- (dimethylamino)ethyl methacrylate-random-1-pyrenylmethyl methacrylate) P3HT- b-P(DMAEMA-r-PyMA).1 Synthesis of conjugated diblock polymer P3HT-b-P(DMAEMA-r-PyMA)61 3.2 Optical and thermal properties of conjugated diblock copolymer P3HT-b- P(DMAEMA-r-PyMA) and sensory application 0.3 Synthesis of 4-(2-ethylhexyl)-2-(pyren-1-yl)-4h-dithieno[3,2-b:2',3'-d]pyrrole (EP4HP) and 4-(2-ethylhexyl)-2,6-di(pyren-1-yl)-4h-dithieno[3,2-b:2',3'-d]pyrrole 91502017177.1 Synthesis and characterization of EP4HP and EDP4HP.2 Application of EP4HP and EDP4HP for tracing mesotfrione.4 Synthesis of donor-acceptor conjugated copolymers poly(alkyl-POZ-DPP) and poly(benzoylalkyl-POZ-DPP) via direct arylation polycondensation (compound P1 b)18 220191; 0 .41 Synthesis of monomer 10-(2-ethylhexyl)-10H-phenoxazine (M1) and monomer 10-(4-(hexyl)benzoyl)-10H-phenoxazine (M2).2 Synthesis of polymers poly(alkyl-POZ-DPP) (P1) and poly(benzoylalkyl- POZ-DPP) (P2).3 Structure of polymers poly(alkyl-POZ-DPP) (P1) and poly(benzoylalkyl- I197/219)12007217 071010080.4 Optical Properties of polymers poly(alkyl-POZ-DPP) (PI) and poly(benzoylalkyl-POZ-DPP) (P2). s9 ng Hư,9] CHAPTER 4 CONCLUSION AND RECOMMENDA TION.2 Contributions Of this H€S1S.-- 5 G5 + 11v 9n TT ng ng94 4.3 Recommendations and development directions .- 5 5< £+s£+ssse+sxe 95 LIST OF PUBLICATIONS.- HH HH HH HH nghệ 96 3585450105002. 98 XI LIST OF FIGURES Figure 1.

Schematic of the bonds of carbon in a conjugated polymer. The electrons in m-molecular orbitals are delOCaÌÏ1Z€C.-- «6 5c +11 1911121119111 1111 9111 TH ng tr 3 Figure 1. The common conducting polymer sfTUCfUTG.-- 5 +55 <++£+scx+ee++ 4 Figure 1. The common conducting polymer SfTUCfUTG.

Current-Voltage (I-V) curves of an PSCS. Schematic of the top-contact configuration (a) and top-gate structure (b) of Figure 1. Output characteristic for a P3HT OFET with L = 0. -- -- c2 11H TH ng HH HH kg 12 Figure 1.

Regiochemical isomers Of P3 A ϧ.- 5 + 13v ng re 14 Figure 1. P3HT structure and AFM picture of P3HÏF. Typical ligands for Cu-based ATRP. FT-IR spectrum of 2-hydroxyethyl methacrylate (HEMA) (black line) and IP.

'H NMR spectrum of DCTMA (CDC]:, 25 °C, 500 MHZ). 'H NMR of P3HT-H and P3HT-Macroinitiator in CHC]:. FT-IR spectrum of P3HT-macroinitiator (A) and diblock copolymer P3HT- 1489 09//. 'H NMR spectrum of diblock copolymer P3HT-b-PDCTMA (P1).

GPC traces of P3HT-macroinitiator (red short dash line) and diblock copolymer P3HT-b-PDCTMA (black solid line) (A); plot of diblock copolymers conversion vs. time demonstrating the control over polymerization propagation (B) and dependence of molecular weight (Mn, GPC) on monomer conversion (C). 'H NMR spectra recorded in CDC]: of diblock copolymer P2. 'H NMR spectra recorded in CDCI; of diblock copolymers P3.

'H NMR spectra recorded in CDC] of diblock copolymers P4. 'H NMR spectra recorded in CDCI; of diblock copolymers P5. Absorption spectra of polymer PI (A), P2 (B), P3 (C), P4 (D), P5 (E) in differenf SOÏV€TIfS .