Title Page
Contents
PART Ⅰ. Substituent effect on difluoroboron complexes and its application as nitro aromatics sensing materials 18
ABSTRACT 19
INTRODUCTION 21
EXPERIMENTAL 23
General information 23
Synthesis procedures 23
Crystal structure determination 25
Absorption and fluorescence measurements 26
Fluorescence quantum yield and fluorescence lifetime 26
DFT calculations 26
Cyclic voltammetry measurements 26
RESULTS AND DISCUSSION 28
Synthesis and X-ray structures 28
Photophysical properties and DFT calculations 30
Electrochemical properties 33
Chemosensor application 34
CONCLUSION 37
REFERENCE 38
PART Ⅱ. Strong σ-hole activation on icosahedral carborane derivatives for a directional halide recognition 62
ABSTRACT 63
INTRODUCTION 65
EXPERIMENTAL 67
General information 67
Synthesis procedures 67
Cocrystallization and crystal structure determination 69
Theoretical calculations 71
RESULTS AND DISCUSSION 74
Synthesis and X-ray structure 74
Cocrystallization 75
CONCLUSION 79
REFERENCE 80
PART Ⅲ. Electron accepting PDI-Cb interlayer for over 22% inverted perovskite solar cells with photo- and thermal stability 105
ABSTRACT 106
INTRODUCTION 108
EXPERIMENTAL 111
General information 111
Synthesis procedures 112
Absorption and fluorescence measurements 113
DFT calculations 113
Cyclic voltammetry measurements 114
Device fabrication 114
Device characterization 115
RESULTS AND DISCUSSION 117
Synthesis 117
Photophysical properties 117
Electrochemical properties 119
Device performance 119
CONCLUSION 125
REFERENCE 126
국문요약 144
PUBLICATION LIST 146
PART Ⅰ. Substituent effect on difluoroboron complexes and its application as nitro aromatics sensing materials 9
Table Ⅰ-1. Crystal data and structure refinement for BF₂dbm–F. 59
Table Ⅰ-2. Photophysical properties of BF₂dbm-F, BF₂dbm-H, and BF₂dbm-OMe. 60
Table Ⅰ-3. Main transitions obtained from TDDFT calculations. 61
Table Ⅰ-4. Electrochemical properties of BF₂dbm-F, BF₂dbm-H, and BF₂dbm-OMe. 61
PART Ⅱ. Strong σ-hole activation on icosahedral carborane derivatives for a directional halide recognition 12
Table Ⅱ-1. Crystallographic data of 1, 2, 1-Br, 2-Cl, 3-I, and 3-Br. 102
Table Ⅱ-2. VS,max (kcal/mol) on the 0.001 a.u. isodensity molecular surfaces associated with the X=I, Se & Te σ-holes opposite to the Ccarborane-X and CMe-X bonds...[이미지참조] 103
Table Ⅱ-3. VS,max (kcal/mol) on the 0.001 a.u. isodensity molecular surfaces for dicyanodiselenide and bis(pnitrophenyl)diselenide.[이미지참조] 103
Table Ⅱ-4. Chalcogen bond characteristics in 2-Cl. 104
PART Ⅲ. Electron accepting PDI-Cb interlayer for over 22% inverted perovskite solar cells with photo- and thermal stability 17
Table Ⅲ-1. Selected electronic transitions from the TD-DFT calculations for PDI-Cb. 142
Table Ⅲ-2. Summary of photovoltaic properties of inverted perovskite solar cells with 0, 1.0, 2.0 and 3.0 nm PDI-Cb interlayer. 142
Table Ⅲ-3. Photovoltaic parameters of inverted PSCs with and without PDI-Cb interlayer before and after 1000 h-stability-test under simultaneous 1 Sun light... 143
PART Ⅰ. Substituent effect on difluoroboron complexes and its application as nitro aromatics sensing materials 8
Figure Ⅰ-1. ¹H (a) and ¹³C (b) NMR spectra of BF₂dbm-F in CD₂Cl₂ 44
Figure Ⅰ-2. ORTEP-III [1] structure of BF₂dbm–F at 30% probability for the thermal ellipsoids. Hydrogen atoms were omitted for clarity. 45
Figure Ⅰ-3. Molecular structure (a), packing diagram (b), and the three types of intermolecular interactions (c) of BF₂dbm-F. 46
Figure Ⅰ-4. UV/Vis absorption (solid line) and emission (dashed line) spectra of BF₂dbm-F (a), BF₂dbm-H (b), and BF₂dbm-OMe (c) in 10 μM chloroform solution... 47
Figure Ⅰ-5. Absorption spectra of BF₂dbm-F (a), BF₂dbm-H (b), and BF₂dbm-OMe (c) measured in various solvents. 48
Figure Ⅰ-6. Emission spectra of BF₂dbm-F (a), BF₂dbm-H (b), and BF₂dbm-OMe (c) measured in various solvents. 49
Figure Ⅰ-7. Fluorescence lifetime decay profile of BF₂dbm-F, BF₂dbm-H, and BF₂dbm-OMe in chloroform solution at room temperature. 50
Figure Ⅰ-8. HOMO and LUMO distributions and energy levels (eV) (a) and theoretical absorption spectra (b) for BF₂dbm-F, BF₂dbm-H, and BF₂dbm-OMe... 51
Figure Ⅰ-9. Cyclic voltammograms of BF₂dbm-F (black), BF₂dbm-H (red), and BF₂dbm-OMe (blue) in 1 mM dichloromethane containing 0.1 M n-Bu₄NPF₆ as an... 52
Figure Ⅰ-10. Repeat voltammograms of BF₂dbm-F (a), BF₂dbm-H (b), and BF₂dbm-OMe (c) at 100 mV/s in dichloromethane solution containing 0.1 M n-Bu₄NPF₆. 53
Figure Ⅰ-11. Normalized absorption spectrum of o-NA (black) and emission spectra of BF₂dbm-F (red), BF₂dbm-H (blue), and BF₂dbm-OMe (green) in 10 μM... 54
Figure Ⅰ-12. Fluorescence quenching of BF₂dbm-F (a), BF₂dbm-H (b), and BF₂dbm-OMe (c) (1 μM) upon addition of different concentrations of o-NA (0–500... 56
Figure Ⅰ-13. The Stern–Volmer plots of BF₂dbm-F, BF₂dbm-H, and BF₂dbm-OMe at a various concentration of o-NA (a–c) and at lower concentrations (d). 58
PART Ⅱ. Strong σ-hole activation on icosahedral carborane derivatives for a directional halide recognition 11
Figure Ⅱ-1. ¹H (a), ¹³C (b) and ¹¹B (c) NMR spectra of 1 in CDCl₃. 91
Figure Ⅱ-2. ¹H (a), ¹³C (b) and ¹¹B (c) NMR spectra of 2 in CDCl₃. 93
Figure Ⅱ-3. Superimposition of the experimental (carbon as grey), B3LYP-D3 (carbon as green) and M062X (carbon as red) optimized molecular structures of bis(p-... 94
Figure Ⅱ-4. Molecular packing in 1 at 298 K. (Yellow spheres: Se, gray spheres: C, and pink spheres: B atoms); H atoms are omitted for clarity. 95
Figure Ⅱ-5. Molecular packing in 2 at 298 K. (Light brown spheres: Te, gray spheres: C, pink spheres: B, blue spheres: H atoms); H atoms, except for those (H2) engaged... 96
Figure Ⅱ-6. X-ray crystal structure of [(1)Br]– in 1-Br, collected at T=298 K. (Yellow spheres: Se, red sphere: Br, gray spheres: C, and pink spheres: B atoms); H... 97
Figure Ⅱ-7. Detail of two independent chalcogen bonding chains running along the a and b directions, respectively, in 2-Cl. (Brown spheres: Te, green spheres: Cl, gray... 98
Figure Ⅱ-8. Detail of halogen-bonded 1D network running along the b direction in 3-Ⅰ. (Purple spheres: I, gray spheres: C, and pink spheres: B atoms); H atoms and Bu4N⁺... 99
Figure Ⅱ-9. Detail of halogen-bonded dimeric molecular unit in 3-Br. (Purple spheres: I, red spheres: Br, gray spheres: C, and pink spheres: B atoms); H atoms and... 99
Figure Ⅱ-10. Computed electrostatic potential of 1 (a), 2 (b), and 3 (c) on the 0.001 electron/bohr3 contour of the electronic density. The extrema values Vs,max of the...[이미지참조] 100
Figure Ⅱ-11. ESP mapped on the 0.001 a.u. isodensity surface of 1 (Se); the ESP range (red: 0.0 / blue 13.8 kcal/mol) is chosen to highlight the second σ-hole that is... 100
Figure Ⅱ-12. ESP mapped on the 0.001 a.u. isodensity surface of 2 (Te); the ESP range (red: 0.0 / blue 21.3 kcal/mol) is chosen to highlight the second σ-hole that is... 101
PART Ⅲ. Electron accepting PDI-Cb interlayer for over 22% inverted perovskite solar cells with photo- and thermal stability 15
Figure Ⅲ-1. ¹H NMR spectrum of PDI-Cb in CDCl₃. 134
Figure Ⅲ-2. MALDI-TOF spectrum for PDI-Cb. 134
Figure Ⅲ-3. UV/Vis absorption (black) and normalized PL emission (red) spectra (λex=560 nm) for PDI-Cb in 10 μM dichloromethane at 298 K.[이미지참조] 135
Figure Ⅲ-4. The optimized structures of PDI-Cb (a) and selective molecular orbital energies and surfaces (b). 135
Figure Ⅲ-5. Measured UV/Vis absorption spectrum in dichloromethane and the calculated absorption spectrum and oscillation strengths for PDI-Cb using... 136
Figure Ⅲ-6. Cyclic voltammogram of PDI-Cb in dichloromethane solution containing 0.1 M n-Bu₄NPF₆ as electrolyte, at a scan rate of 0.1 V s¯¹. 136
Figure Ⅲ-7. a) Scanning electron microscope (SEM) cross-sectional image of inverted PSCs composed of ITO/PTAA/perovskite/PDI–Cb/C₆₀/BCP/Ag, b) current... 137
Figure Ⅲ-8. Band energy level diagram of inverted PSC with PDI-Cb interlayer. 138
Figure Ⅲ-9. The J-V curves of the inverted PSCs introduced with 1.0 nm and 3.0 nm PDI-Cb interlayer. 138
Figure Ⅲ-10. Box plots of the photovoltaic parameters across 50 samples of inverted PSCs introduced with different thickness of PDI-Cb interlayer. 139
Figure Ⅲ-11. UV-Vis spectra and their corresponding Tauc plots of control (glass/perovskite) and PDI-Cb (glass/perovskite/2.0 nm PDI-Cb) samples. 139
Figure Ⅲ-12. Static PL spectra of (a) control sample and (b) PDI–Cb sample and TRPL spectra (c): perovskite=glass/perovskite, control=ITO/PTAA/perovskite/C₆₀,... 140
Figure Ⅲ-13. Current density–voltage curves of unencapsulated PSCs with a) 2.0nm PDI–Cb interlayer and b) without interlayer (control) and the c) corresponding... 141
Scheme Ⅰ. Synthesis of BF₂dbm-F, BF₂dbm-H, and BF₂dbm-OMe. 43
Scheme Ⅱ. Synthesis of 1-3. (Gray spheres: C, pink spheres: B atoms) 89
Scheme Ⅲ. Synthesis of PDI–Cb: i) Pd(PPh₃)₄, K₂CO₃, THF/H₂O, reflux, yield: 12%, ii) decaborane, DMF, 100 °C, overnight, yield: 40%. 133