Making crystals by design : methods, techniques and applications
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1 Geometry and Energetics. 1.1 Supramolecular Interactions: Energetic Considerations (Angelo Gavezzotti). 1.1.1 Introduction. 1.1.2 Enthalpy. 1.1.3 Entropy. 1.1.4 Free Energy. 1.1.5 Tutorial Examples. 1.2 Understanding the Nature of the Intermolecular Interactions in Molecular Crystals. A Theoretical Perspective (Juan J. Novoa, Emiliana D'Oria, and Maria A. Carvajal). 1.2.1 Introduction. 1.2.2 Intermolecular Interactions. 1.2.3 Summary. 1.3 Networks, Topologies, and Entanglements (Lucia Carlucci, Gianfranco Ciani, and Davide M. Proserpio). 1.3.1 Introduction. 1.3.2 Rationalization and Simplification of the Extended Structures. 1.3.3 Topological Classification of Networks. 1.3.4 Entangled Systems. 1.3.5 Conclusions. 2 Design and Reactivity. 2.1 Prediction of Reactivity in Solid-state Chemistry (Gerd Kaupp). 2.1.1 Introduction. 2.1.2 Topochemistry and Topotaxy. 2.1.3 Far-reaching Molecular Migrations in Solid-state Reactions (AFM, GID, SNOM) and Experimental Solid-state Mechanism. 2.1.4 Face Selectivity of Reactivity. 2.1.5 Some of the Important Failures of Topochemistry and Their Remedy by the Experimental Mechanism. 2.1.6 Molecular Migrations in the Absence of Severe Local Pressure. 2.1.7 Multiple Cleavage Planes. 2.1.8 Various Types of Cleavage Planes. 2.1.9 Channels. 2. 1.10 Closed Voids. 2. 1.11 Interpretation of Some Recent Literature Data. 2. 1.12 Applications in Addition to Solid-state Syntheses. 2. 1.13 Conclusions and Outlook. 2.2 Making Crystals by Reacting Crystals (Fumio Toda). 2.2.1 Introduction. 2.2.2 Thermal Solid-state Reactions. 2.2.3 Making Inclusion Complex Crystals by Mixing or Grinding Host and Guest Crystals. 2.2.4 Making Crystals by Phase Transition. 2.2.5 Control of Differential Inclusion Complexation by Seed Crystals. 2.2.6 Conclusions. 2.3 Making Crystals by Reactions in Crystals. Supramolecular Approaches to Crystal-to-Crystal Transformations within Molecular Co-Crystals (Tomislav Friscic and Leonard R. MacGillivray). 2.3.1 Introduction. 2.3.2 Single-component Solids. 2.3.3 Co-crystals. 2.3.4 SCSC Reactivity by Modifying Experimental Conditions. 2.3.5 Conclusion. 2.4 Making Coordination Frameworks (Neil R. Champness). 2.4.1 Introduction. 2.4.2 Coordination Framework Design Criteria. 2.4.3 Coordination Polymer Design Approaches. 2.4.4 Synthetic Considerations and Approaches. 2.4.5 Structural Evaluation and Analysis. 2.4.6 Structural Description. 2.4.7 Conclusions. 2.5 Assembly of Molecular Solids via Non-covalent Interactions (Christer B. Aakercy and Nate Schultheiss). 2.5.1 Introduction. 2.5.2 Directed Assembly of Homomeric Molecular Solids. 2.5.3 Design and Synthesis of Co-crystals. 3 Characterizations and Applications. 3.1 Diffraction Studies in Crystal Engineering (Guillermo Minguez Espallargas and Lee Brammer). 3.1.1 Introduction. 3.1.2 Scope. 3.1.3 Single Crystal X-ray Diffraction. 3.1.4 Single crystal neutron diffraction. 3.1.5 Single Crystal Diffraction Studies at Low Temperatures. 3.1.6 Single Crystal Diffraction Studies at Increased Pressures. 3.1.7 Powder Diffraction. 3.1.8 Charge Density Studies. 3.1.9 Conclusions. 3.2 Solid State NMR (Roberto Gobetto). 3.2.1 Introduction. 3.2.2 The Fundamentals. 3.2.3 CPMAS. 3.2.4 Advantages and Disadvantages of Solid State NMR Spectroscopy. 3.2.5 Polymorphism. 3.2.6 Resolution of Enantiomers by Solid State NMR. 3.2.7 Distances Determined by SSNMR. 3.2.8 Hydrogen Bond. 3.3 Crystal Polymorphism: Challenges at the Crossroads of Science and Technology (Dario Braga and Joel Bernstein). 3.3.1 Introduction. 3.2.2 How Do We Detect and Characterize Multiple Crystal Forms? 3.3.3 New Developments in Detecting and Characterizing Multiple Crystal Forms. 3.3.4 Examples of Crystal Form Identification and Characterization. 3.3.5 Practical Implications and Ramifications of Multiple Crystal Forms - Pharmaceuticals. 3.3.6 Conclusions. 3.4 Nanoporosity, Gas Storage, Gas Sensing (Satoshi Takamizawa). 3.4.1 Introduction. 3.4.2 Description of Porosity. 3.4.3 Nanoporosity for Gas Adsorption. 3.4.4 Brief Thermodynamic Description of the Gas Adsorption Phenomenon. 3.4.5 Crystalline Organic and Metal-Organic Gas Adsorbents. 3.4.6 Dawn of Metal-Organic Gas Adsorbents. 3.4.7 Design of Porosity in Coordination Polymer Systems. 3.4.8 Structural Description and Dimensionality of the Host Component. 3.4.9 Transformation of a Single-crystal Gas Adsorbent during Gas Adsorption. 3. 4.10 Abnormal Guest Diffusivity Within Pores. 3. 4.11 Method for the Accurate Detection and Measurement of the Gas Adsorbed State. 3. 4.12 Hydrogen Storage [21]. 3. 4.13 Phase Transition of the Adsorbed Guest Sublattice in the Gas Inclusion Co-crystal State [23]. 3. 4.14 Dynamic Change in Pore Topology by Design of Host Flexibility [24]. 3. 4.15 Mass-induced Phase Transition [24]. 3. 4.16 Sensing Gas by Porous Crystals. 3. 4.17 Concluding Remarks.