Eastern Illinois University The Keep Masters Theses Student Theses & Publications 2017 Functionalized BODIPY Dyes for Near-Infrared Emission of Lanthanide Complexes Rukshani Wickrama Arachchi Eastern Illinois University This research is a product of the graduate program in Chemistry at Eastern Illinois University. Find out more about the program. Recommended Citation Arachchi, Rukshani Wickrama, "Functionalized BODIPY Dyes for Near-Infrared Emission of Lanthanide Complexes" (2017). Masters Theses. 2911. https://thekeep.eiu.edu/theses/2911 This is brought to you for free and open access by the Student Theses & Publications at The Keep. It has been accepted for inclusion in Masters Theses by an authorized administrator of The Keep. For more information, please contact [email protected]. The GraduateSchool .EASTEH.N ILLINOISUNIVERSITY­ � Tbesis Maintenance and Reproduction Certificate FOR: Graduate Candidates Completing Theses in Partial Fulfillment of the Degree Graduate Faculty Advisors Directing the Theses RE: Preservation, Reproduction, and Distribution of Thesis Research Preserving, reproducing, and distributing thesis research is an important part of Booth Library's responsibility to provide access to scholarship. In order to further this goal, Booth Library makes all graduate theses completed as part of a degree program at EasternIllinois University available for personal study, research, and other not-for-profit educational purposes. Under 17 U.S.C. § 108, the library may reproduce and distribute a copy without infringing on copyright; however, professional courtesy dictates that pennission be requested from the author before doing so. Your signatures affirm the following: • The graduate candidate is the author of this thesis. • The graduate candidate retains the copyright and intellectual property rights associated with the original research, creative activity, and intellectual or artistic content of the thesis. • The graduate candidate certifies her/his compliance with federal copyright law (Title 17 of the U. S. Code) and her/his right to authorize reproduction and distribution of all copyrighted materials included in this thesis. • The graduate candidate in consultation with the faculty advisor grants Booth Library the non­ exclusive, perpetual right to make copies of the thesis freely and publicly available without restriction, by means of any current or successive technology, including by not limited to photocopying, microfilm, digitization, or internet. • The graduate candidate acknowledges that by depositing her/his thesis with Booth Library, her/his work is available for viewing by the public and may be borrowed through the library's circulation and interlibrary loan departments, or accessed electronically. • The graduate candidate waives the confidentiality provisions of the Family Educational Rights and Privacy Act (FERPA) (20 U. S. C. § l 232g; 34 CFR Part 99) with respect to the contents of the thesis and with respect to information concerning authorship of the thesis, including name and status as a student at Eastern Illinois University. I have conferred with my graduate faculty advisor. My signature below indicates that I have read and agree with the above statements, and hereby give my permission to allow Booth Library to reproduce and distribute my thesis. My adviser's signature indicates concurrence to reproduce and distribute the thesis. Graduate Candidate Signature F')l'l\'l)y Adviser Signature Printed Name Printed Name fl1a..skr DP gc.�Vlc. CkHYl'�H; in I Graduate Degree Program Date Please submit in duplicate. BODIPY Functionalized dyes for Near-infrared Emission of Lanthanide Complexes (TITLE) BY Rukshani Wickrama Arachchi THESIS SUBMITIED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science in Chemistry IN THE GRADUATE SCHOOL, EASTERN ILLINOIS UNIVERSITY CHARLESTON, ILLINOIS 2017 YEAR I HEREBY RECOMMEND THAT THIS THESIS BE ACCEPTED AS FULFILLING THIS PART OF THE GRADUATE DEGREE CITED ABOVE 7/t11/� l}'ESISCOMMITTEE CHAIR DATE DEPARTMENT/SCHOOL CHAIR DATE OR CHAIR'S DESIGNEE THESIS COMMITTEE MEMBER 3iJJDATE /J7- THESIS COMMlfTEE MEMBER DATE 10/11 THESIS COMMITTEE MEMBER DATE THESIS COMMITTEE MEMBER DATE Functionalized BODIPY Dyes for Near-infrared Emission of Lanthanide Complexes Rukshani Wickrama Arachchi Research Advisor: Dr. Hongshan He Eastern Illinois University Chemistry Department TABLE OF CONTENTS TABLE OF CONTENTS .................................... ................... ............... ...i ABBREVIATIONS ............................................................................. vi ABSTRACT .......................................................................................vii ACKNOWLEDGEMENTS .................................................... ...... .... .....vii i LIST OF FIGURES . ................. ............................ .... .. ....... ..........ix LIST OF TABLES .......... .......... ...................... .... ............... .....xiv CHAPTER 1 INTRODUCTION 1 1.1. Overview 2 1.2. Luminescence 3 1.2.1. Fluorescence 1.2.1.1. Light-Matter Interaction 3 1.2.1.2. Emission Process 4 1.2.1.3. Excitation Spectrum 5 1.2.1.4. Emission Sp ectrum 5 1.2.1.5. Fluorescence Quantum Efficiency 7 1. 2.1. 6. Lifetime of Excited State 8 1.2. 1. 7. Factors Affecting fo r the Fluorescence Intensity 8 1.2.1. 8. limitations of Fluorescence 9 10 1.2.2. Phosphorescence 1 1.2.3. Fluorophores for Medical Diagnosis I 15 1.3. Fundamentals of Lanthaoides 16 1.3.1. Physical Properties l.3.2. Chemical Properties 16 1.3.3. Formation of Complexes 18 1.4. NIR Emitting Lanthanide Complexes 21 1.4.1. NIR Emission 21 1.4. 1. l. lanthanide NIR Emission 21 1.4.1.2. Energy Transfer Mechanism in lanthanide Organic Complex 23 1.4.2. Lanthanide Complexes 24 1.4.2.1. DOTA Complexes 24 1.4.2.2. Porphyrin Complexes 28 1.4.2.3. Phenanthroline Complexes 31 1.4.2.4. BOD/P Y Based Lanthanide Complexes 34 1.4.3. Applications of NIR Emitting Lanthanides 38 1.5. Motivation 41 1.6. Objectives 42 43 CHAPTER 2 SYNTHESIS & MEASUREMENTS 43 2.1. General 43 2.1.1. Materials 44 2.1.2. Instruments 45 2.2. Synthesis 2.2.1. Project 1 Synthetic Route 45 2.2.J. 1. Synthesis of RHl 46 2.2.1.2. Synthesis of RH2 47 2.2.1.3. Synthesis of RH3 48 ii 2.2. 1.4. Synthesis of RH4 49 2.2.1.5. Synthesis of RH5 50 2.2.J.6. Synthesis of RH6 51 2.2.1.7. Synthesis ofRH 7 52 2.2. 1.8. Synthesis of RHB 53 2.2. 1.9. Synthesis of RH9 54 2.2.2. Project 2 Synthetic Route 55 2.2.2.1. Synthesis of RHJO 56 2.2.2.2. Synthesis of RHII 57 2.2.2.3. Synthesis of RHI 2 58 2.2.2.4. Synthesis of RHl3 59 2.2.2.5. Synthesis of RHl4 60 2.2.2.6. Synthesis of Complex 1 61 2.2.2. 7. Synthesis of Complex 2 62 2.3. PhotophysicaJ Measurements 62 2.3.1. UV-VIS Absorption Spectra in Solutions 62 2.3.2. Fluorescence Spectra 63 2.3.2. 1. Excit ation and Emis sion Spect ra 63 2.3.2.2. Qu antum Yield Measu rements 64 2.3.3. Lifetime Measurements 65 2.3.3.J. Lifeti me Measu rement inthe Visib le Regio n 65 2.3.3.2. Lifetime Measu rement inthe NJR Region 65 2.3.4. Spectroscopic Titration 65 iii CHAPTER 3 RES UL TS AND DISCUSSION 67 3.1. Characterization 67 3.1.1. NMR Spectroscopy 67 3. 1.1.1. 1HNMR of Compound RH/ 67 3.1.1.2. 1HNMR of Compound RH2 68 3.1.1.3. 1HNMR of Compound RH3 69 3. 1. 1.4. 1HNMR of Compound RH4 70 3.1.1.5. 1H NM R of Compound RH5 71 3. 1. 1.6. 1HNMR of Compound RH6 72 3. 1. 1.7. 1HNMR of Compound RH7 73 3. 1.1.8. 1HNMR of Compound RH8 74 3. 1.1.9. 1HNMR of Compound RH9 75 3. 1.1.10. 1HNMR of Compound RHJO 76 3. 1.1.11. 1HNMR of Compound RH/ 1 77 3. 1.1. 12. 1HNM R of Compound RH12 78 3. 1. 1.13. 1HNMR o/Compound RHJ3 79 3. 1. 1. 14. 1HNM R of Compound RH14 80 3.1.2. X-Ray Crystallography 82 3.2. Photophysical Properties 89 3.2.1. Photophysical Properties of Ligands 89 3.2.1.1. Absorption Data 89 3.2.1.2. Fluorescence Data 89 3.2.1.3. Quantum Yield Measurements 90 iv 3.2. 1.4. lifetime Measurements 98 3.2.2. Photophysical Properties of Lanthanide Complexes 99 3.2.2.1. Interaction of RH12 with [Yb{TPP)(OAc)(MeOH)2] in CH2Cli 100 (formation of complex 1) 3.2.2.2. Interaction of RHJ4 with [Yb{TPP)(OAc)(MeOH)2] in CH2C'2 101 (formation of complex 2) 3.2.2.3. Spectroscopic Titrations with RH12 and RH14 Ligands 102 3.2.2.4. Lifetime at NIR Region 105 CHAPTER 4 CONCLUSION 107 REFERENCES 109 APPENDICES 118 v ABBREVIATIONS I. BODIPY - boron-dipyrromethene 2. NIR - near-infrared 3. NMR-nuclear magnetic resonance 4. TMS - tetramethylsilane 5. DOTA -1,4,7,10-tetraazacyclododecane- I,4,7, I O-tetraacetic acid 6. DTPA - diethylenetriaminepentaacetic acid 7. TFA - trifluoroacetic acid 8. Ln - lanthanide 9. TCSCT - time-correlated single photon counting technique 10. CAFS - chemoselective alteration of fluorophore scaffolds 11. TRL - time-resolved luminescent 12. TRLM - time resolved luminescence microscopy 13. MRI - magnetic resonance imaging 14. PET - photoinduced electron transfer 15. LLBs - lanthanide luminescent bioprobes 16. TPP - tetraphenylporphyrin 17. HMRG - hydroxymethyl rhodamine green 18. TMOS - tetramethoxysilane 19. Por - Porphyrin vi ABSTRACT For many decades, fluorophores have been used to investigate natural systems, but autofluorescence and photobleaching diminish the detection capacity. Recently, BODIPY based lanthanide complexes have been synthesized and their photophysical properties have been investigated. These complexes exhibit higher emission efficienciesat NIR region with longer NIR lifetimes upon exciting at longer wavelength. In this study, two BODIPY based lanthanide complexes were synthesized and their photophysical properties were evaluated. BODIPY based ligands were synthesized with phenanthroline as the ligand binding group. These ligands exhibit strong absorption at 527 nm and 532 nm, fluorescence at 540 nm and 548 nm with 0.55 (±0.0l) and 0.78 (±0.06) quantum yields.