Novel Luminescent Crystalline Materials of Gold(I) Complexes with Stimuli-Responsive Properties (eBook)

Supervisor’s Foreword 6
Contents 8
1 General Introduction 12
1.1 External Stimuli Responsive Luminescence of Solid-State Molecular Materials 12
1.2 Luminescence Properties of Gold(I) Complexes 16
1.3 Conditions for Crystal-to-Crystal/Single-Crystal-to-Single-Crystal Transformation 17
1.4 Features of Biaryl Group 17
1.5 Chirality of Molecular Crystal and Wallach’s Rule 18
1.5.1 Chirality of Molecular Crystal 18
1.5.2 Wallach’s Rule 19
1.6 Amphidynamic Crystal 20
References 23
2 Biphenyl Moiety for a Solvent Responsive Aryl Gold(I) Isocyanide Complex with Reactivation by Mechanical Grinding 27
2.1 Introduction 27
2.2 Synthesis and Observed Mechanochromism 32
2.3 Emission Color Changes Induced by Solvent Addition and Grinding 32
2.4 Single-Crystal Structure Analyses 37
2.5 Structure–Property Relationship 43
2.6 Summary 45
2.7 Experimental Section 45
2.7.1 General 45
2.7.2 Synthesis 46
2.7.3 Optical Properties of 3 in Solution Phase 47
2.7.4 Changes of 3/solvent in Response to Mechanical Stimulation 48
2.7.5 Solvents Response of 3ground 49
2.7.6 Changes of 3/solvent in Response to Mechanical Stimulation 49
2.7.7 Changes of 3/solvent upon Heating Under Reduced Pressure 49
2.7.8 Data for Single-Crystal X-ray Structural Analyses 63
2.7.9 Comparison of the Powder Samples and the Single Crystals of 3/solvent 66
2.7.10 The Single-Crystal Structure of 3/none 66
2.7.11 TD-DFT Calculations of 3/CHCl3, 3/CH2Cl2, and 3/acetone 77
References 88
3 Luminescent Mechanochromism of a Chiral Complex: Distinct Crystal Structures and Color Changes of Racemic and Homochiral Gold(I) Isocyanide Complexes with a Binaphthyl Moiety 92
3.1 Introduction 92
3.2 Synthesis and Preparation 93
3.2.1 Synthesis of (rac)-1 and (S)-1 94
3.2.2 Preparation of the Single Crystals of (rac)-1G and (S)-1G 95
3.3 Single Crystal X-ray Diffraction (XRD) Analyses 95
3.4 Studies of Crystal Structure Alterations by Mechanical Stimulation 97
3.5 Luminescent Mechanochromism of (rac)-1G and (S)-1G 98
3.6 Summary 100
3.7 Experimental Section 101
3.7.1 General 101
3.7.2 Optical Properties of Solution Phase 101
3.7.3 Photophysical Properties of Each Solid Phase 101
3.7.4 TGA Profiles 101
3.7.5 NMR Spectra and Elemental Analysis 103
3.7.6 The CH2Cl2 Release by Heating Under Vacuum from (rac)-1G and (S)-1G 104
3.7.7 Crystal Structures of (rac)-1G and (S)-1G 106
References 109
4 Mechano-Responsive Luminescence via Crystal-to-Crystal Phase Transitions Between Chiral and Non-chiral Space Groups 112
4.1 Introduction 112
4.2 Synthesis and Preparation 115
4.2.1 Synthesis 116
4.2.2 Preparation of 1ch and 1ac from 1o 119
4.3 Single Crystal XRD Analyses of 1ch and 1ac 119
4.4 Studies on Mechano-Induced Crystal Structure Alterations 122
4.5 Thermal Analyses 122
4.6 Luminescent Properties and Mechano-Responsive Luminescence 124
4.7 Summary 126
4.8 Experimental Section 126
4.8.1 General 126
4.8.2 Data for Single-Crystal X-ray Structural Analyses 127
4.8.3 PXRD Patterns and Simulated Powder Patterns of 1ch and 1ac 127
4.8.4 Photophysical Properties 127
4.8.5 TD-DFT Calculations of 1ch and 1ac 129
4.8.6 Optical Properties of Solution Phase 131
4.8.7 Evaluation of Changes of 1gournd After Ceased Grinding 131
References 134
5 Mechanical-Stimulation-Triggered and Solvent-Vapor-Induced Reverse Single-Crystal-to-Single-Crystal Phase Transitions with Alterations of the Luminescence Color 136
5.1 Introduction 136
5.2 Synthesis and Preparation 138
5.3 Single Crystal X-ray Diffraction Analyses 140
5.4 Studies on Luminescence Properties 142
5.5 Control Experiment and Proposed Mechanism of the Reversible SCSC 145
5.6 Summary 146
5.7 Experimental Section 147
5.7.1 General 147
5.7.2 Synthesis 147
5.7.3 Preparation of Crystals of 3G/MeOH and 3O 149
5.7.4 Procedures for Crystal Cutting and Changing MeOH Vapor Concentrations 150
5.7.5 Data for Single Crystal X-ray Structural Analyses 151
5.7.6 1H NMR Spectra of 3G/MeOH and 3O 151
5.7.7 TGA and Elemental Analysis of 3O 153
5.7.8 Photophysical Properties 153
5.7.9 Changes of the Luminescence After Exposure to External Stimuli 155
5.7.10 Mechanochromic Luminescence of Powder Samples 156
5.7.11 SEM Images of the 3O Samples Prepared by Various Procedures 159
5.7.12 DFT Calculations of 3G/MeOH and 3Oscsc 159
5.7.13 Analysis of Polarity in Crystals 3G/MeOH and 3Oscsc 162
References 163
6 Thermo-Responsive Phosphorescence Control Mediated by Molecular Rotation and Aurophilic Interactions in Amphidynamic Crystals of Phosphine-Gold(I) Complex 166
6.1 Introduction 166
6.2 Synthesis and Characterization 168
6.3 Single Crystal X-ray Diffraction and Thermal Analyses of 1 and 2 169
6.4 Crystallinity and Phase Identity of Powdered Samples 174
6.5 Variable Temperature Solid State NMR Studies of 1-d4 and 2 175
6.6 Emission Properties of 1 and 2 177
6.7 Potential Correlation Between Triplet Decay and Rotational Dynamics 180
6.8 Summary 183
6.9 Experimental Section 183
6.9.1 General 183
6.9.2 Synthesis 184
6.9.3 TGA of 1 and 2 185
6.9.4 Data for Single-Crystal X-ray Structural Analyses 185
6.9.5 DSC of 1 and 2 186
6.9.6 Solid-State NMR Studies of 1 and 2 186
6.9.7 Optical Properties of Solution Phase 189
6.9.8 TD-DFT Calculations 190
6.9.9 Photophysical Properties 193
References 198