Eastern Illinois University The Keep Masters Theses Student Theses & Publications 2017 BODIPY-based Red Sensitizers for Near-infrared Emission of Lanthanide Complexes Priyangika Prasadini Senevirathne 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 Senevirathne, Priyangika Prasadini, "BODIPY-based Red Sensitizers for Near-infrared Emission of Lanthanide Complexes" (2017). Masters Theses. 2744. https://thekeep.eiu.edu/theses/2744 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]. 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BODIPY-based Red Sensitizers for Near-infrared Emission of Lanthanide Complexes (TITLE) BY Priyangika Prasadini Senevirathne THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUREMENTS 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 THESIS COMMITTEE CHAIR DATE DEPARTMENT/SCHOOL CHAIR DATE OR CHAIR'S DESIGNEE S:-/:l. ./J ? 0.r/l?/7Vtr ' � IBESIS COMMITTEE MEMBER DATE THESIS COMMITTEE M€MBER DA TE Wf'RSISICOMMITTEE MEMBER DATE BODIPY-based Red Sensitizers for Near-infrared Emission of Lanthanide Complexes PRIYANGIKA PRASADINI SENEVIRATHNE Research Advisor: Dr. Hongshan He Department of Chemistry Eastern Illinois University ii TABLE OF CONTENTS TABLE OF CONTENTS ............................................................................................................ iii ABBREVIATIONS ..................................................................................................................... vii ABSTRACT ................................................................................................................................ viii ACKNOWLEDGEMENTS ......................................................................................................... x LIST OF FIGURES ..................................................................................................................... xi LIST OF TABLES .................................................................................................................... xvii INTRODUCTION......................................................................................................................... 1 1.0 General Overview ................................................................................................ 1 1.1 Phenomena of Fluorescence ................................................................................. 2 1.2 Characteristics of Fluorescence ................................................................................. 4 1.2.1 Representation of fluorescence data ................................................................... 4 1.2.2 Stokes shift ......................................................................................................... 4 1.3 Applications of Fluorescence ... ... .......... ... ........... ........ ................. .......... ........ 5 1.3.1 Fluorescence sensing and fluorescence probes .................................................. 6 1.4 BODIPY dyes . ................. ..................... ............ ........... ................. ............. ....... ....... 7 1.4.1 Synthesis of BODIPY dyes ................................................................................ 9 1.4.2 Modification of BODIPY core ........................................................................... 9 1.4.2.l Functionalization at the 2,6-positions of BODIPY core ........ ....................... 9 iii 1.4.2.2 Sonogashira coupling reaction ................................................................... 11 1.5 Lanthanide Luminescence ....................................................................................... 12 1.5 .1 Lanthanide luminescence efficiency ................................................................ 14 1.5.2 Lanthanide complexes ...................................................................................... 15 1.5.2.1 Porphyrinbased lanthanide complexes ...................................................... 16 1.5 .1.2 8-hydroxyquinoline based lanthanide complexes ...................................... 20 1.5.1.3�-Diketonate based lanthanide complexes .................................................. 22 L5.l.4 BODIPY based lanthanide complexes ....................................................... 24 1.6 Motivation ............................................................................................................... 30 1.7 Objectives ........................................................................................................... 31 EXPERIMENTAL ...................................................................................................................... 32 2.1 General .................................................................................................................... 32 2.1.1 Materials ........................................................................................................... 32 2.1.2 Instrumentation ................................................................................................. 33 2.2 Synthesis .................................................................................................................. 34 2.1.1 Synthesis ofC19H19BF2N2 (PS 001) ................................................................. 35 2.2.2 Synthesis of C19H1sBF2IN2 (PS002) ................................................................. 36 2.2.3 Synthesis of C 13H10N2 (PS003) ......................................................................... 3 7 2.2.4 Synthesis of C32H21BF2N4 (ligand PHI) .......................................................... 38 2.2.5 Synthesis of C32H26BF2IN4 (ligand PH2) ......................................................... 39 iv 2.2.6 Synthesis of C41H3 1BF2N402 (ligand PH3) ...................................................... 40 2.2.7 Synthesis of C9HsNS (PS004) .......................................................................... 41 2.2.8 Synthesis ofC 41H30BF2NsS (ligand PH4) ........................................................ 41 2.2.9 Synthesis ofC 24H21BF2N2Si (PS005) ............................................................... 42 2.2.10 Synthesis of C21H19Bf2 N2 (PS006) ................................................................ 43 2.2.11 Synthesis of ytterbium complexes .................................................................