The Nature of Ultralong C-C Bonds

Description

This book focuses on the creation and demonstration of a carbon–carbon (C–C) single bond beyond 1.8 Å and on elucidation of its unique nature. C–C single bond is one of the most fundamental concepts in organic chemistry. The elucidation of its nature is important for further understanding chemical phenomena. The nature in the extreme state of C–C single bond is still unexplored because of the instability of compounds. In terms of its bond length, the limit had been predicted around 1.8 Å based on the experimental and theoretical studies. This book describes a first example of a C–C single bond beyond 1.8 Å by employing the original intramolecular core-shell strategy to make a weak and elongated bond stable enough. The presence of such an elongated bond was demonstrated by experimental and theoretical studies. The bond length changes could affect physical properties such as optical absorption and redox potential. Furthermore, its unique "flexibility" was discovered. This book benefits the chemists with deeper understanding of the covalent bonding. Cover Springer Theses Series The Nature of Ultralong C–C Bonds Copyright Supervisor’s Foreword Parts of this thesis have been published in the following journal articles Acknowledgements Contents 1. General Introduction 1.1 C–C Covalent Bond 1.2 Unusual Bonding Interaction 1.3 Short and Long C–C Single Bond References 2. Creation and Demonstration of the Longest C–C Single Bond with a Bond Length Beyond 1.8 Å 2.1 Introduction 2.2 Results and Discussions 2.2.1 Design Concept 2.2.2 Theoretical Examination for Molecular Design 2.2.3 Preparation of Hydrocarbon 1a–1c 2.2.4 Raman Spectroscopy 2.2.5 Experimentally Determined Bond Length by X-ray Analyses 2.2.6 Stability of the Hydrocarbon 1c with a Very Weak C–C Bond 2.2.7 Theoretical Analysis for the Nature of Ultralong C–C Single Bond 2.3 Conclusion 2.4 Experimental Section References 3. Discovery of Flexible Bonds Based on an Extremely Elongated C–C Single Bond 3.1 Introduction 3.2 Results and Discussions 3.2.1 Intramolecular Photocyclization 3.2.2 Theoretical Study 3.2.3 Single-Crystal-to-Single-Crystal Transformation 3.2.4 Redox Behavior 3.3 Conclusion 3.4 Experimental Section References Curriculum Vitae