University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Spring 2011 Chemistry of acenes, [60]fullerenes, cyclacenes and carbon nanotubes Chandrani Pramanik University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation Pramanik, Chandrani, "Chemistry of acenes, [60]fullerenes, cyclacenes and carbon nanotubes" (2011). Doctoral Dissertations. 574. https://scholars.unh.edu/dissertation/574 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]. CHEMISTRY OF ACENES, [60]FULLERENES, CYCLACENES AND CARBON NANOTUBES BY CHANDRANI PRAMANIK B.Sc., Jadavpur University, Kolkata, India, 2002 M.Sc, Indian Institute of Technology Kanpur, India, 2004 DISSERTATION Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Materials Science May 2011 UMI Number: 3467368 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMI Dissertation Publishing UMI 3467368 Copyright 2011 by ProQuest LLC. All rights reserved. This edition of the work is protected against unauthorized copying under Title 17, United States Code. ProQuest LLC 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 A En P. Miller, Dissertation director Pribfessor of Chemistry and Materials science J c\ MO m • E • 'f "^ '-p~»~~ James E. Harper Professor of Physics and Materials Science ;/\ ./ Donald C. Sundberg / Emeritus Professor of Materials/ Science ^A_2^b5' Richard P. Johnson Professor of Chemistry Karsten Pohl Professor of Physics and Materials Science Date "If I find 10,000 ways something won't work, I haven't failed. I am not discouraged, because every wrong attempt discarded is another step forward". —Thomas Edison "Failure is the opportunity to begin again more intelligently." — Henry Ford in ACKNOWLEDGEMENTS My thesis would be incomplete without expressing my sincere gratitude to certain individuals. I owe my deepest gratitude to my advisor Prof. Glen Miller for his guidance, patience and endorsement, both intellectually and financially. I would never forget his consolations during one of those depressed days because of some failed reaction. But I want to thank him the most for providing me the opportunity to work in the various fields of materials science ranging from organic chemistry to nanotechnology. It was always great to learn from his amazing ability to channel his enthusiasm on a particular topic through his talks. I want to dedicate my thesis to my parents Mrs. Ashrukana Pramanik and Late Joy Narayan Pramanik whose blessings and inspiration still drag me the most. I would not have been able to walk this journey alone without the constant support and immense enthusiasm of my sister Dr. Indrani Pramanik and my brother-in-law Dr. Nilay Kundu, channeled through all those long distance telephone calls. I can never thank enough my husband Jishnu Bhattacharyya for his constant encouragement. The tiniest bit of success in my research often excited him more than me. He even gave me company sometimes when I was at work late at night. I would also like to express my sincerest thanks to my parents-in-law Dr. Saurindramohan Bhattacharyya and Mrs. Tapati Bhattacharyya and by brother-in-law Pratyush Bhattacharyya for their blessings and love. iv I feel honored to have Prof. James Harper, Prof. Richard Johnson, Prof. Karsten Pohl and Prof. Donald Sundberg in my thesis committee. Collaborating with Prof. Harper was a wonderful learning experience. Prof. Johnson's computation course has significantly contributed to my overall chemistry education. I am fortunate to have Prof. Harper, Prof. Johnson, Prof. Miller, Prof. Sundberg and Prof. Charles Zercher as my teachers for various courses. My heartiest thanks go to Dr. Ryan Kopreski for being my computation guru. Without his help, a large part of my research would have remained incomplete. Ryan has been tremendously helpful to me during the preparations of this thesis, as well as with my review paper and proposal earlier. He is always available to discuss chemistry whenever the need be. I would like to thank Jon Briggs for a very thorough review of my thesis. Thanks to Yushu Li for helping me with the last few clean-up reactions, to Yi Xu for always being so supportive and to Jeremy Kintigh, Julia Chan, Simka Ellis, Dr. Jennifer Hodgson, Shunfu Hu, Dr. Weimin Lin, James Roane and Lei Zhou for discussions on research and random stuff. The contribution of some past members of the Miller group towards my doctoral research is undeniable. It is a pleasure to acknowledge the help of Dr. Irvinder Kaur, Dr. Wenling Jia and Dr. Michael Jadzyk for training me on several critical and sensitive organic syntheses as well as various analytical tools. I also want to thank Eman Akam, Dr. Andrew Athans, Joe Dunn, Dr. Jun-fu Liu, Polina Prusevich, Dr. James Rainbolt, Elizabeth Stairs and Nathan Stein for always being helpful and cooperative. v Often when I felt deluded about chemistry, friendship kept it real. I am really thankful to my friends at UNH, Dr. Dana Filoti, Elizabeth Garcia, Srinivas Guntur, Parikshit Junnarkar, Faraz Mehdi, Manasi Patil and Dr. Aveek Sarkar for being by my side. When things did not go right, it was always refreshing to talk to my buddies Dr. Samanwita Pal, Karishma Jain, Susmita Basak, Debasmita Chaki, Manikarnika Kanjilal, Payel Samanta and Saikat Chakraborti Thakur. I am indebted to my friends Dr. Priya Iyer and Dr. Anandarup Goswami for their priceless help in fetching me some valuable literature. I am very thankful to Cindi Rower and Peg Torch for being so kind and helpful on innumerable occasions. My sincere thanks go to Bob Constantine for his willingness and eagerness to help all the time, to Cathy Gallagher, Dr. Patricia Wilkinson and John Wilderman for always finding the time to teach me various analytical techniques including NMR, and to Nancy Cherim and Mark Townley for teaching me how to handle the TEM and the SEM. Last but not the least I thank "National Science Foundation" and "Center for the High-rate Nanomanufacturing" for funding me throughout my Ph.D career. Thank you for reading my thesis! VI TABLE OF CONTENTS ACKNOWLEDGEMENTS IV TABLE OF CONTENTS VII LIST OF FIGURES XI LIST OF SCHEMES XV LIST OF TABLES XVIII LIST OF MOLECULES XX ABSTRACT XXX CHAPTER 1 1 1. SYNTHESIS AND STUDY OF ACENES, SUBSTITUTED ACENES, AND ACENE QUINONES 1 1.1 Introduction 1 1.1.1 Syntheses and State of the Art Applications of Acenes and Functionalized Acenes 2 1.1.1.1 Anthracene 3 1.1.1.2 Substituted Anthracenes and Their Applications 4 1.1.1.2.1 FETs with Functionalized Anthracenes 5 1.1.1.2.2 OLEDs with Anthracene Derivatives 7 1.1.1.2.3 Solar Cells with Functionalized Anthracenes 9 1.1.1.3 Tetracene 10 1.1.1.4 Substituted Tetracenes and Their Applications 11 1.1.1.5 Pentacene and Its Applications 15 1.1.1.5.1 FETs and Charge Carrier Mobility of Pentacene 17 1.1.1.5.2 Recent Advances with Pentacene in Other Applications 21 1.1.1.5.3 Drawbacks of Pentacene 22 1.1.1.6 Scope of Functionalized Pentacenes 23 1.1.1.6.1 FETs orTFTs of Functionalized Pentacenes 25 1.1.1.6.2 Other Applications of Functionalized Pentacenes 29 1.1.1.7 Larger Acenes 31 1.1.1.7.1 Hexacene 32 1.1.1.7.2 Functionalized Hexacenes 32 1.1.1.7.3 Heptacene 33 vii 1.1.1.7.4 Functionalized Heptacenes 35 1.1.1.7.5 Octacene, Nonacene and Functionalized Nonacenes 37 1.1.2 Theory behind Chemistry and Electronic Properties of Acenes 39 1.1.2.1 Stability and Reactivity of Acenes 39 1.1.2.2 Comparative Study of Reactivity of Acenes 40 1.1.2.3 Photodegradation of Acenes 41 1.1.2.4 HOMO-LUMO Energy and Band Gap of Acenes 43 1.2 Results and Discussion 48 1.2.1 Sulfur Stabilized Pentacene Derivatives 48 1.2.1.1 Synthesis of 3,3'-(Pentacene-6,13-diylbis(sulfanediyl))dipropanoic acid, an Intermediate for Making A Molecular Switch 48 1.2.1.1.1 Synthesis 49 1.2.1.2 Synthesis of S,S'-Pentacene-6,13-diyl diethanethioate, an Intermediate for Making Pentacene Oligomers with Disulfide Linkages 54 1.2.1.2.1 Synthesis 55 1.2.1.3 Pentacene-6,13-Disulfonium Salt 59 1.2.1.3.1 Attempts to Synthesize 6,13-Bis(n-dodecylthio)pentacene 61 1.2.1.4 Attempted Synthesis of 2,3,9,10-Tetrakis(benzylthio)-6,13- bis(phenylthio)pentacene 66 1.2.1.5 Theoretical Study of Thio-substituted Pentacenes 69 1.2.1.6 Conclusions and Future Work 71 1.2.2 Synthesis of Sulfur and Chloro Substituted Anthracene 72 1.2.2.1 Synthesis of 9,10-Bis(phenylthio)anthracene 72 1.2.2.2 Application to [60]Fullerene and Carbon Nanotubes 75 1.2.2.3 Future Direction and Conclusions 76 1.2.3 Towards the Synthesis of Larger Acenes; Sulfur-Stabilized Nonacene 76 1.2.3.1 Attempt to Synthesize 1,4,8,12,15,19-Hexa(4'-^-butylphenylthio)nonacene 78 1.2.3.2 Theoretical Studies of Arylthio Substituted Nonacenes 85 1.2.3.3 Conclusions and Future Direction 86 1.2.4 Spectroscopic Studies of Acene Quinones and Hydroxyacenes in Concentrated Sulfuric Acid 87 1.2.4.1 UV-Vis-NIR Study of Acene Derivatives in Concentrated Sulfuric Acid 88 vin 1.2.4.2 Proposed Mechanism 94 1.2.4.3 Conclusions and Future Direction 96 CHAPTER 2 97 2.