Fragments of Fullerenes and Carbon Nanotubes

This book is the first of its kind to reflect upon the intense and rapidly growing interest in open geodesic polyaromatic molecules, specifically focusing on their synthesis and reactivity in metal binding reactions. The book broadly covers all aspects related to the fullerene fragment chemistry: current synthetic techniques, description of the available members of this new family (which has grown to more than two dozens members, with none being available commercially), molecular geometry and trends in the solid state packing, as well as extensions into physical properties and new buckybowl-based molecules and materials. It covers fundamental research related to a new class of hydrocarbons, namely open geodesic polyarenes that map onto the surfaces of fullerenes (and referred to as fullerene fragments or buckybowls. PREFACE vii

FOREWORD xi

CONTRIBUTORS xiii

ACRONYMS xvii

1 MOLECULAR CLIPS AND TWEEZERS WITH CORANNULENE PINCERS 1
Andrzej Sygula and Willard E. Collier

2 SYNTHESIS OF BOWL-SHAPED AND BASKET-SHAPED FULLERENE FRAGMENTS VIA BENZANNULATED ENYNE---ALLENES 41
Kung K. Wang, Hu Cui, and Bo Wen

3 ANIONS OF BUCKYBOWLS 63
David Eisenberg, Roy Shenhar, and Mordecai Rabinovitz

4 CURVED p-CONJUGATED STABLE OPEN-SHELL SYSTEMS POSSESSING THREE-DIMENSIONAL MOLECULAR/ELECTRONIC SPIN STRUCTURES 95
Yasushi Morita and Akira Ueda

5 EXPERIMENTAL AND CALCULATED PROPERTIES OF FULLERENE AND NANOTUBE FRAGMENTS 135
Derek R. Jones, Praveen Bachawala, and James Mack

6 COORDINATION PREFERENCES OF BOWL-SHAPED POLYAROMATIC HYDROCARBONS 157
Alexander S. Filatov and Marina A. Petrukhina

7 SUMANENES: SYNTHESIS AND COMPLEXATION 187
Toshikazu Hirao and Toru Amaya

8 r-BONDED TRANSITION METAL COMPLEXES OF POLYCYCLIC AROMATIC CARBON COMPOUNDS 205
Paul R. Sharp

9 HEMISPHERICAL GEODESIC POLYARENES: ATTRACTIVE TEMPLATES FOR THE CHEMICAL SYNTHESIS OF UNIFORM-DIAMETER ARMCHAIR NANOTUBES 235
Anthony P. Belanger, Katharine A. Mirica, James Mack, and Lawrence T. Scott

10 AROMATIC BELTS AS SECTIONS OF NANOTUBES 259
Gaston R. Schaller and Rainer Herges

11 CYCLOPARAPHENYLENES: THE SHORTEST POSSIBLE SEGMENTS OF ARMCHAIR CARBON NANOTUBES 291
Xia Tian and Ramesh Jasti

12 CONJUGATED MOLECULAR BELTS BASED ON 3D BENZANNULENE SYSTEMS 311
Masahiko Iyoda, Yoshiyuki Kuwatani, Tohru Nishinaga, Masayoshi Takase, and Tomohiko Nishiuchi

13 TOWARD FULLY UNSATURATED DOUBLE-STRANDED CYCLES 343
Malte Standera and A. Dieter Schl€uter

14 BENT PYRENES: SPRINGBOARDS TO AROMATIC BELTS? 367
Graham J. Bodwell, Gandikota Venkataramana, and Unikela Kiran Sagar

INDEX 401

“Despite the many exciting papers published since this book became available in 2012, this monograph will be a valuable addition to any library, an enjoyable page turner for aficionados of hydrocarbon chemistry, and a treasure trove for advanced students of organic chemistry.” (Chemistry International, 1 May 2013)

Marina A. Petrukhina received her PhD from Moscow State University in 1988 and is a Professor in the Department of Chemistry at the University of Albany. She has published over 120 research papers in scientific journals. In 2006, she received the NSF Career Award, a five-year grant to explore the reactivity and coordination limits of open geodesic polyaromatic hydrocarbons (buckybowls).

Lawrence T. Scott received his PhD from Harvard University in 1970 and is a Professor at Boston College, where he occupies the Louise and Jim Vanderslice and Family Chair in Chemistry. He has published more than 200 research papers in scientific journals and currently serves on the editorial advisory boards for Polycyclic Aromatic Compounds and The Journal of Organic Chemistry. In 2011, he received the George A. Olah Award in Hydrocarbon Chemistry from the American Chemical Society.

Open geodesic polyaromatic molecules, or "buckybowls": new research findings, syntheses, and reactions

The day is rapidly approaching when scientists will have the tools necessary to exploit the tremendous potential of carbon nanotubes, fullerenes, and endohedral fullerene complexes of predetermined structures. Reviewing the latest research into geodesic polyaromatic molecules, this contributed work focuses on their synthesis and reactivity in metal-binding reactions. Readers will find expert coverage of all aspects of fullerene fragment chemistry, including current synthetic techniques, molecular geometry, solid state packing, physical properties, and new buckybowl-based molecules and materials. Readers will also discover the implications of the latest fundamental research examining open geodesic polyarenes that map onto the surfaces of fullerenes.

The first part of this book describes research on the synthesis, chemistry, properties, and potential applications of various fullerene fragments and their derivatives. The second half of the book focuses on the development of methods needed for the rational chemical synthesis of single-chirality, uniform-diameter carbon nanotubes. Individual topics include:

• Molecular clips and tweezers with corannulene pincers

• Anions of buckybowls

• Coordination preferences of bowl-shaped polyarenes

• Experimental and calculated properties of fullerene and nanotube fragments

• Synthesis and complexation of sumanenes

• Aromatic belts as sections of nanotubes

• Conjugated molecular belts based on 3-D benzannulene systems

Each chapter, written by one or more leading investigators in the field, presents the latest research breakthroughs in North America, Europe, and Asia, offering not only a review of the current literature, but also perspectives from the authors' first-hand experience in the lab. As a result, readers can confidently turn to this book to advance their own investigations into the synthesis, reactions, and coordination chemistry of fullerene fragments and carbon nanotubes.