A comprehensive review to the synthesis, properties, and applications of diarylethene-based molecular photoswitches

Diarylethene Molecular Photoswitches: Concept and Functionalities provides the fundamental concepts of molecular photoswitches and includes information on how the bistable photoswitches of diarylethenes modulate the functions of materials and biological activities. Written by Masahiro Irie (the inventor of photochromic diarylethene compound), the book explores the reaction mechanism, photoswitching performance, photoswitchable crystals, and the myriad applications of diarylethenes based photoswitches.

This book offers academics, chemists, and engineers an essential resource for understanding the molecular photoswitches and provides a guide to the development of new photoresponsive materials. The author explores the applications based on diarylethene and its dirivatives to Field-Effect Transistors, Metal-Organic Frameworks including nanoparticles, super-resolution fluorescence microscopies, drug release, and self-healing materials. This important book:

* Offers a guide to diarylethene derivatives, the most widely studied compounds worldwide among the photochromic compounds
* Includes the basic concepts of molecular photoswitches
* Explores the myraid applications grounded in diarylethene and its derivatives
* Presents an authortative text from the inventor of the photochromic diarylethene compound

Written for materials scientists, organic, polymer, and physical chemists, and electronics engineers, Diarylethene Molecular Photoswitches offers an introduction to the topic and includes recent developments in the field.

Masahiro Irie is an emeritus professor of Kyushu University. He received his B.S. and M.S. from Kyoto University and his Ph.D. in radiation chemistry from Osaka University. In 1968 he joined the Faculty of Engineering, Hokkaido University, as a research associate and started his research in photochemistry. He was the faculty members of at Osaka University, Kyushu University and Rikkyo University. He has been conducting research on molecular photoswitch systems for more than 40 years. In the middle of the 1980s he discovered thermally irreversible and fatigue resistant photochromic diarylethenes. Prof. Irie has authored over 500 scientific publications and has received numerous scientific awards, including Porter Medal (European Photochemistry Association, The Inter-American Photochemistry Society and Asian and oseanian Photochemsitry association), Theodor-Foerster-Preis (GDCh and Deutsche Bunsen-Gesellschaft, Germany) and The Chemical Society of Japan Award.

Preface ix

1 Introduction1

1.1 General Introduction 1

1.2 Discovery of Diarylethene Molecular Photoswitches 4

References 12

2 Reaction Mechanism15

2.1 Basic Concepts 15

2.2 Theoretical Study 20

2.3 Reaction Dynamics 22

2.3.1 Cyclization Reaction 22

2.3.2 Cycloreversion Reaction 27

References 29

3 Photoswitching Performance31

3.1 Quantum Yield 31

3.1.1 Photocyclization Quantum Yield 31

3.1.2 Solvent Effect on Cyclization Quantum Yield 42

3.1.3 Photocycloreversion Quantum Yield 44

3.2 Thermal Stability 49

3.3 Fatigue Resistance 53

3.4 Fluorescence Property 60

3.4.1 Turn-Off Mode Photoswitching 61

3.4.2 Turn-On Mode Photoswitching 76

3.5 Chiral Property 80

References 86

4 Photoswitchable Crystals93

4.1 Dichroism 93

4.2 X-Ray Crystallographic Analysis 97

4.3 Quantum Yield 101

4.4 Multicolored Systems and Nano-Layered Periodic Structures 106

4.5 Fluorescent Crystals 108

4.6 Photomechanical Response 110

4.6.1 Surface Morphology Change 112

4.6.2 Reversible Shape Change 113

4.6.3 Bending Response of Mixed Crystals 116

References 121

5 Memory125

5.1 Single-Molecule Memory 125

5.2 Near-Field Optical Memory 128

5.3 Three-Dimensional Optical Memory 130

5.4 Readout Using Infrared Absorption, Raman Scattering, and Refractive Index Changes 132

References 134

6 Switches137

6.1 Single-Molecule Conductance Photoswitch 137

6.2 Optical Switch Based on Refractive Index Change 141

6.3 Magnetism 141

References 146

7 Surface Properties149

7.1 SurfaceWettability 149

7.2 Selective Metal Deposition 151

7.3 Subwavelength Nanopatterning 154

References 155

8 Polymers and Liquid Crystals157

8.1 Polymers 157

8.2 Liquid Crystals 175

References 178

9 Applications183

9.1 Organic Field-Effect Transistors (OFETs) 183

9.2 Metal Organic Frameworks (MOFs) 185

9.3 Super-Resolution Fluorescence Microscopy 188

9.3.1 Control of Cycloreversion Quantum Yield 189

9.3.2 Fatigue Resistance 191

9.3.3 Photoswitching with Single-Wavelength Visible Light 192

9.3.4 Super-Resolution Bioimaging 195

9.4 Chemical Reactivity Control 197

9.5 Biological Activity 201

9.6 Color Dosimeters 204

References 209

A Synthesis Procedures of Typical Diarylethenes213

A.1 1,2-Bis(2,4-dimethyl-5-phenyl-3-thienyl)perfluorocyclopentene 213

A.2 1,2-Bis(2-ethyl-6-phenyl-1-benzothiophene-1,1-dioxide-3-yl)-perfluorocyclopenetene 215

References 217

Index 219