© 2015 by Taylor & Francis Group, LLC © 2015 by Taylor & Francis Group, LLC (cid:49)(cid:66)(cid:79)(cid:1)(cid:52)(cid:85)(cid:66)(cid:79)(cid:71)(cid:80)(cid:83)(cid:69)(cid:1)(cid:52)(cid:70)(cid:83)(cid:74)(cid:70)(cid:84)(cid:1)(cid:80)(cid:79)(cid:1)(cid:51)(cid:70)(cid:79)(cid:70)(cid:88)(cid:66)(cid:67)(cid:77)(cid:70)(cid:1)(cid:38)(cid:79)(cid:70)(cid:83)(cid:72)(cid:90)(cid:1)(cid:137)(cid:1)(cid:55)(cid:80)(cid:77)(cid:86)(cid:78)(cid:70)(cid:1)(cid:19) ORGANIC STRUCTURE DESIGN APPLICATIONS IN OPTICAL AND ELECTRONIC DEVICES editors PrebenMaegaard AnnaKrenz edited by WolfgangPalz Tahsin J. Chow The Rise of Modern Wind Energy Wind Power for the World © 2015 by Taylor & Francis Group, LLC CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2015 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Version Date: 20141104 International Standard Book Number-13: 978-981-4463-35-5 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources. Reason- able efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www. copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organiza- tion that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Contents Preface 1. Theoretical Modeling for Electron Transfer in Organic xiii Materials 1 Robert C. Snoeberger III, Bo-Chao Lin, and Chao-Ping Hsu 1.1 Introduction 1 1.1.1 Theoretical Modeling for Electron Transfer in Solar Cells 3 1.1.1.1 The influence of energy gaps 3 1.1.1.2 Charge separation and recombination 4 1.1.2 Theoretical Modeling for Charge Transport 7 1.1.2.1 The hopping models 7 1.1.2.2 Polaron models 10 1.2 Electronic Coupling 11 1.2.1 Structural Models 12 1.2.1.1 Idealized models 12 1.2.1.2 Crystal structures 13 1.2.1.3 Simulated morphology 14 1.2.2 Calculation of Electronic Coupling 14 1.2.2.1 Energy gap 15 1.2.2.2 Direct coupling 17 1.2.2.3 The generalized Mulliken–Hush and fragment charge difference schemes 20 2. Organic Structure Design and Applications in Solution-Processed 1.3 Conclusion 23 Organic Micro- and Nanomaterials 33 Ting Lei, Jie-Yu Wang, and Jian Pei 2.1 Introduction 34 2.2 Main Approaches to Organic Micro/Nanomaterials 35 © 2015 by Taylor & Francis Group, LLC vi Contents 2.2.1 Template Synthesis 36 2.2.2 Electrospinning 37 2.2.3 Lithography 39 2.2.4 Physical Vapor Transport 40 2.2.5 Solution Process 43 2.2.5.1 Vapor diffusion 43 2.2.5.2 Phase transfer 44 2.2.5.3 Rapid solution dispersion 44 2.2.5.4 Sol-gel process 45 2.3 Molecular Design Strategy for Solution Processed p p Organic Micro/Nanomaterials 45 2.3.1 – Interaction 45 2.3.2 Donor–Acceptor Interaction 48 2.3.3 Sulfur–Sulfur Interaction 49 2.3.4 Hydrophobic Interaction 51 2.3.5 Hydrogen-Bonding Interaction 52 2.4 Impact Factors and Growth Mechanism of Organic p p Micro/Nanomaterials 54 2.4.1 Alkyl Chain Effect and – Stacking 54 2.4.2 Isomeric Effect and Solvent Effect 56 2.4.3 Organic Microtwist and Temperature Effect 59 2.4.4 Organic Micro/Nanotube Formed by Etching 60 2.4.5 Organic Flowers Formed by Hierarchical Self-Assembly 61 2.4.6 “Oriented Attachment” Mechanism 64 2.5 Applications of Organic Micro/Nanomaterials 66 2.5.1 Organic Field-Effect Transistors 66 2.5.2 Organic Light-Emitting Diodes and Organic Photovoltaics 71 2.5.3 Photodetector 72 2.5.4 Photowaveguide 73 2.5.5 Gas and Explosive Detection 75 2.5.6 Superhydrophobic Material 76 2.6 Surface Modification of Organic Micro/ Nanomaterials 77 2.7 Summary and Perspectives 79 © 2015 by Taylor & Francis Group, LLC Contents vii 3. Synthesis, Structure, and Electronic and Photophysical Properties of Donor–Acceptor Cyclophanes 95 Masahiko Shibahara, Motonori Watanabe, Takaaki Miyazaki, Jun-ichi Fujishige, Yuki Matsunaga, Keisuke Tao, Zhang Hua, Kenta Goto, and Teruo Shinmyozu 3.1 Introduction 95 3.2 Structural, Photophysical, and Charge Transfer Interaction of Multilayered [3.3]Paracyclophanes 100 3.3 Synthesis, Structure, Electronic, and Photophysical and Properties of [2.2]Benzothiadiazolophane 115 3.4 Synthesis, Structure, Electronic and Photophysical Properties of Two- and Three-Layered [3.3]Paracyclophane-Based Donor–Acceptor Systems 122 4. 3Li.5gh t- Caonndc Elulescitornic aitnyd-G Fautetudr Ien tReermnaalr Rkost ation of Molecular 130 Rotors: Toward Artificial Molecular Machines 137 Jye-Shane Yang and Wei-Ting Sun cis-trans 4.1 Introduction 137 4.2 Photoisomerization 141 4.3 Chemicals-Gated Molecular Brakes 152 4.4 Light-Gated Molecular Brakes 160 4.5 Electricity-Gated Molecular Brakes 168 5. 4S.u6p ramCoonleccluudlainr gA sRseemmabrlkiess aonfd O Prgearnspoegcetlisv Feesa turing 172 p-Conjugated Framework with Long-Chain Dicarboxamides 185 M. Rajeswara Rao and Shih-Sheng Sun 5.1 Introduction 186 5.2 Classification of Gels 186 5.2.1 Organogelators Based on Elongated Hydrocarbons, Fatty Acids, and Esters 188 5.2.2 Organogelators Based on Saccharides 189 5.2.3 Organogelators Based on Steroids 190 5.2.4 Organogelators Based on Aromatic Molecules 190 © 2015 by Taylor & Francis Group, LLC viii Contents 5.2.5 Binary Organogelators 191 5.2.6 Metal Complex Based Organogelators 193 5.2.7 Organogelators Based on Amino Acids and Ureas 194 5.3 Organogelators Based on Amides 196 6. Quinoxaline-Based Polycyclic Molecules Having Defined 5.4 Conclusions 220 Shapes: From Orthocyclophanes to Polyazaacenes 229 Teh-Chang Chou 6.1 Introduction 229 6.2 Prologue 232 nn¢ 6.3 U- and Z-Shaped Multi-Bridged [ , ]Orthocyclophanes 235 6.3.1 The Quadruple-Bridged [5,5]Orthocyclophanes and [6,6]Orthocyclophanes 236 6.3.2 The U-Shaped Septuple-Bridged [7,7]Orthocyclophanes 242 pp 6.3.3 The Z-Shaped [6,4]Orthocyclophanes 248 6.4 N-Shaped , -Stacking Molecules 252 6.5 Multi-Functionalized Polyazaacenes 259 6.5.1 Multi-Functionalized Chlorinated Polyacenoquinone Esters 261 6.5.2 Mechanistic Consideration for Fragmentation of Chlorinated Polyacenoquinone Esters 268 6.5.3 Amination of Chlorinated Polyacenoquinone Esters 272 7. Fluorogenic Sensors of Heavy Metal Ions Based on 6.6 Closing Remarks 275 Calix[4]arenes Functionalized by 1,3-Dipolar Cycloaddition Reactions 287 Wen-Sheng Chung 7.1 Introduction of Calixarenes 287 7.2 1,3-Dipolar Cycloaddition Reactions and Subsequent Ring-Opening Reactions 290 © 2015 by Taylor & Francis Group, LLC Contents ix 7.3 Calix[4]arenes with Upper- and Lower-Rim Isoxazolines and Isoxazoles 293 7.4 Fluorogenic Sensors of Calix[4]arenes with Lower-Rim 1,2,3-Triazoles 299 7.5 Metal Ion Sensing and Ditopic Sensing Based on Calix[4]arenes Functionalized by 1,3-Dipolar Cycloaddition Reactions 309 8. 7E.l6e ctroSnu mTrmanasrpyo arnt dM Paetersripaelsc tiniv eO rganic Light-Emitting 319 Diodes: Design Considerations and Structural Diversity 327 Samik Jhulki, Ishita Neogi, and Jarugu Narasimha Moorthy 8.1 Introduction 327 8.2 Metal Chelates 330 8.3 Six-Membered Heterocycles 332 8.3.1 Pyridines 333 8.3.2 Quinoxaline 336 8.3.3 Naphthyridines 337 8.3.4 Phenanthrolines 338 8.3.5 Pyrazines 340 8.3.6 Pyrimidines 341 8.3.7 Quinoxaline 342 8.3.8 Anthrazolines 344 8.3.9 Triazines 345 8.4 Five-Membered Heterocycles 346 8.4.1 Isobenzofurans 348 8.4.2 Oxazoles 349 8.4.3 Benzimidazoles 349 8.4.4 Benzothiazoles 351 8.4.5 Oxadiazoles 352 8.4.6 Triazoles 354 8.5 Perfluorinated Compounds 356 8.6 Metalloles 359 8.7 Miscellaneous 361 © 2015 by Taylor & Francis Group, LLC x Contents 8.8 Electron-Transporting Materials for Phosphorescent Organic Light-Emitting Diodes 366 8.9 Structural Determinants for Better ETMs: Our Perspective 367 9. Electrochemical Deposition of Carbazole and Triarylamine 8.10 Conclusions and Outlook 389 Derivatives and Their Polymeric Optoelectronic Applications 399 Man-kit Leung 9.1 Introduction 399 9.2 Hole Mobility in Triarylamine-Based Materials 400 9.2.1 Hole-Mobility in Organic Glass 401 9.2.2 Hole-Mobility in Liquid Films 403 9.3 Electrochemical Deposition of Triarylamine-Based Materials 403 9.3.1 Electrochemical Polymerization of Carbazole 405 9.3.2 Electrochemical Polymerization of Dicarbazole, Polycarbazole, and Carbazole Dendrimers 408 9.3.3 Electrochemical Polymerization of Triphenylamine Derivatives 416 9.3.4 Electrochemical Polymerization of Diphenylamine 419 9.3.5 Electrochemical Polymerization of 4-(1-Hydro-xyethyl)Triphenylamine 420 9.3.6 Electrochemical Polymerization of bis(Triphenylamine)s 422 9.3.7 Electrochemical Polymerization of Poly, Hyperbranched, and Dendritic Triphenylamines 428 9.4 Lithography and Nanopatterning 436 9.4.1 Electrochemical Nanolithography 437 9.4.2 Colloidal Template Electropolymerization 438 9.4.3 Electropolymerization of Macromonomer Bearing Photolabile Linker for Imaging 440 © 2015 by Taylor & Francis Group, LLC