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Fullerene-Acene Chemistry University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Spring 2007 Fullerene-acene chemistry: Part I Studies on the regioselective reduction of acenes and acene quinones; Part II Progress toward the synthesis of large acenes and their Diels-Alder chemistry with [60]fullerene Andreas John Athans University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation Athans, Andreas John, "Fullerene-acene chemistry: Part I Studies on the regioselective reduction of acenes and acene quinones; Part II Progress toward the synthesis of large acenes and their Diels-Alder chemistry with [60]fullerene" (2007). Doctoral Dissertations. 363. https://scholars.unh.edu/dissertation/363 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. FULLERENE-ACENE CHEMISTRY: PART I: STUDIES ON THE REGIOSELECTIVE REDUCTION OF ACENES AND ACENE QUINONES; PART II: PROGRESS TOWARD THE SYNTHESIS OF LARGE ACENES AND THEIR DIELS- ALDER CHEMISTRY WITH [60]FULLERENE VOLUME 1 CHAPTERS 1-5 BY ANDREAS JOHN ATHANS B.S. University of New Hampshire, 2001 DISSERTATION Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy m Chemistry May, 2007 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. UMI Number: 3 2 6 0 5 8 6 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. ® UMI UMI Microform 3 2 6 0 5 8 6 Copyright 2007 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, Ml 48106-1346 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. This dissertation has been examined and approved. sertation Director, Glen P. Miller, fessor of Chemistry JZX ?: Richard P. Johnson, Profefeorjbf Chemistry Arthur Greenberg, Professor of Chemistry Steven B. Levery, Associate Professor of C mistry nmpsey7 Professor of Chemistry/ Worcester Polytechnic Institute Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGMENTS First and foremost, I would like to thank my wife, Kristie, for her love, support, patience, and understanding during my entire graduate career. I would also like to thank my two beautiful daughters, Sophia and Stella, for being wonderful little girls who can always bring a smile to my face no matter how stressed or tense I am. I would also like to thank my entire family, especially my parents, for all of their support and understanding. I would like to thank my advisor, Dr. Glen Miller, for his teaching and guidance throughout my chemistry career, both as an undergraduate and throughout graduate school. His enthusiasm for the science was contagious, and we always came up with ideas for some good chemistry to try. I can honestly say that, for all of the immense amounts of chemistry knowledge I gained from all of the professors in this department, I probably learned even more working with Glen over the last seven years. 1 would also like to thank the entire chemistry faculty in the department for delivering a top-notch education for both my undergraduate and graduate careers, especially Professors Weisman, Johnson, Zercher, Wong, and Planalp. I couldn’t have an acknowledgements section without thanking Cindi and Peggy in the office for all of their help over the years, as well as Kathy Gallagher and John Wilderman in the UIC for all of their NMR related help. Also thanks to Bob Constantine for all of his help in the chemistry library finding old journals or microfiches. iii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. I’d like to thank members of the Miller Group past and present, starting with James Mack. James taught me so much about working in the lab when I was working alongside him when I was an undergraduate, and he made it both interesting and fun. I’d like to thank Jon Briggs, who I’ve worked with for the better part of seven years, for being a friend as well as an excellent colleague with whom I could discuss chemistry back and forth. I’d like to thank Carsten Nielsen for being a friend and for sharing the trials and tribulations of finishing our PhD degrees in our many long talks. I’d finally like to thank group members Ryan Kopreski and Jim Rainbolt, as well as fellow graduate students Matt Young, Dan Stigers, Dave Martin, Joon Cho, and Dan Kennedy for being friends and for being people to talk to when graduate school got particularly tough. iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS VOLUME 1 ACKNOWLEDGMENTS....................................................................................................... Hi LIST OF TABLES.................................................................................................................viii LIST OF FIGURES..................................................................................................................ix LIST OF SCHEMES.............................................................................................................. xii LIST OF NUMBERED STRUCTURES............................................................................ xvii ABSTRACT.......................................................................................................................xxxvi CHAPTER 1: INTRODUCTION.............................................................................................1 1.1 Discovery of the Fullerenes .................................................................................. 1 1.2 Chemistry................................................................................................................3 1.2.1 [60]Fullerene .............................................................. 3 1.2.1.1 Recent Advances in the Photochemistry of [60]Fullerene ........................................................................................ 3 1.2.1.2 Biological Applications of [60]Fullerene ............................4 1.2.1.3 Studies Concerning the Regioselectivity of [60]Fullerene Chemistry..............................................................................................7 1.2.1.4 Materials Applications of [60]Fullerene Chemistry..............................................................................................8 1.2.1.5 Cycloaddition Chemistry of [60]Fullerene ........................ 14 1.2.2 Carbon Nanotubes ........................................................16 1.2.2.1 Advances in Preparation of SWNTs ..................................18 v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 1.2.2.2 Advances in Solubilizing and Functionalizing SWNTs................................................................................................19 1.2.2.3 Materials Applications ........................................................ 20 1.3 Acenes ...................................................................................................................22 1.3.1 Properties of the Acenes ...................................................................... 22 1.3.2 Preparation of the Acenes ....................................................................25 1.4 Reactions of [60]Fullerene with Acenes ............................................................39 CHAPTER 2: STUDIES OF REDUCTION OF ACENES AND ACENE QUINONES BY ACTION OF HI AND ACETIC ACID.......................................................................... 45 2.1 Background .......................................................................................................... 45 2.2 Results and Discussion ....................................................................................... 47 CHAPTER 3: STUDIES OF ACENES AND ACENE/[60]FULLERENE CHEMISTRY.......................................................................................................................... 61 3.1 Toward Preparation of Hexaphenyl Nonacene and Tetrakis[60]fullerene Adduct ..........................................................................................................................61 3.2 Toward Preparation of Octaphenyl Undecacene and Pentakis[60]fullerene Adduct ........................................................................................................................ 107 3.3 Preparation of End-Functionalized Pentacenes and Their [60]Fullerene Adducts .....................................................................................................................
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