臺灣博碩士論文加值系統

為了設計多功能的物質含有磁性和螢光性質,我們修飾2,2:6,2-三聯吡啶(Terpy)增加第四取代位置成1-甲基-1H-吡咯-2-基- 2,2:6,2-三聯吡啶。根據先前的研究, 2,2:6,2-三聯吡啶和其螯合過渡性金屬的推電子基或拉電子基能夠影響氧化還原和光物理性質。在此,配位基1-甲基-1H-吡咯-2-基- 2,2:6,2-三聯吡啶(Mtpy)具有分子間電荷轉移性質(共振存在於吡啶和吡咯之間),以致螢光放光光譜波長相較2,2:6,2-三聯吡啶有紅移現象。此外因非輻射的去活化過程,導致隨著溶劑極性增加,量子產率下降。本研究發現一旦配位基鍵結鐵或鈷金屬,其螢光性質便消失,但鋅金屬錯合物沒有此現象。量測Zn(mtpy)2(ClO4)2螢光,所得最強螢光放光在472nm,量子產率為24.84%。

在研究鐵或鈷金屬錯合物螯合1-甲基-1H-吡咯-2-基- 2,2:6,2-三聯吡啶的部分,我們先合成出[M(mtpy)2X2] (M=Fe(II)/Co(II), and X=BF4-)。預期取代一個1-甲基-1H-吡咯-2-基- 2,2:6,2-三聯吡啶成兩個配位基NCS-形成[M(mtpy)(NCS)2]。再進一步合成利用4,4’-聯吡啶連接兩個[M(mtpy)(NCS)2]形成雙金屬錯合物[M(mtpy)(NCS)2-L-M(mtpy)(NCS)2] (L= 4,4’-bipyridine)。把[M(mtpy)2X2] (M=Fe(II)/Co(II), and X=BF4-),[M(mtpy)(NCS)2],and M=Fe錯合物溶於乙睛溶劑養晶,根據單晶繞射數據結果,兩個配位基mtpy螯合金屬且配位基NCS-並未與金屬形成鍵解而是形成陰離子平衡電荷。本研究所合成金屬錯合物皆量測螢光光譜和磁性來探究其物理性質。

In order to design a multifunctional material with magnetic and fluorescent properties, we modify 2,2’:6’,2’’-terpyridine (terpy) to 1-methyl-1H-pyrrol-2-yl-2,2’:6’,2’’-terpyridine(Mtpy) by adding a substituent at 4’-position. Based on previous studies, the electron-withdrawing or electron-releasing substituent can affect redox and photophysical properties of terpyridine and even its chelating with transition metal. In this work, the ligand of mtpy has intermolecular charge-transfer character (the  orbitals conjugation between pyridine and pyrrole units) so that photoluminescence emission spectroscopy displays a red shift effect in comparison with terpy. In addition, the increasing with solvent polarity will also reduce the quantum yield because of the nonradiation decay results. The luminescence property is quenched when the ligand bonds with iron or cobalt metal, but not for zinc complex. The luminescence measurement on Zn(mtpy)2(ClO4)2 indicates the maximum intensity at 472nm with quantum yield 24.84%.

In the study of Fe/Co metal complexes chelating by mtpy, we synthesize the [M(mtpy)2X2] (M=Fe(II)/Co(II), and X=BF4-) first, and then prospectively replace one mtpy by two NCS- ligands to form [M(mtpy)(NCS)2]. Furthermore, linking two [M(mtpy)(NCS)2 ] by 4,4’-bipyridine ligand to form a dinuclear metal complex [M(mtpy)(NCS)2-L-M(mtpy)(NCS)2] (L= 4,4’-bipyridine) is also part of our purpose. We make [M(mtpy)2X2] (M=Fe(II)/Co(II), and X=BF4-), [M(mtpy)(NCS)2] and M=Fe, complexes dissolve acetonitrile solvent to get crystals. Based on the single crystal data results, two mtpy ligands chelating metal and NCS- ligands are not bonding with metal rather than becoming counterions balances charge. The physical properties of these complexes are measured by photo-luminescence spectrum and SQUID.

中文摘要 i
Abstract iii
誌 謝 v
CONTENTS vi
LIST OF TABLES x
LIST OF FIGURES xi
List of Compounds xiv
Chapter 1 INTRODUCTION 1
1.1 The internal charge transfer phenomenon of modified ligands 1
1.2 The UV-Vis and PL spectrum result of ligands 3
1.3 The Spin Crossover Phenomenon 4
1.4 Motivation 4
Chapter 2 THEORY 6
2.1 X-ray Diffraction 6
2.1.1 Introduction 6
2.1.2 In house XRD 7
2.1.3 Synchrotron of XRD 8
2.1.4 Cell constants indexing and space group determination 9
2.2 X-ray Absorption Spectroscopy 10
2.2.1 Introduction 10
2.2.2 X-Ray Absorption Near edge (XANES) 11
2.2.3 The K-edge of XAS 13
2.2.4 Analysis of EXAFS 14
2.3 Infrared Spectroscopy with Attenuated Total Reflectance 16
2.4 Measurement of single crystal 17
2.5 UV-Vis spectroscopy 17
2.6 Photoluminescence spectroscopy 18
Chapter 3 Experiment 19
3.1 Syntheses of Ligand and Metal Complexes 19
3.1.1 Syntheses of 1-methyl-1H-pyrrol-2-yl-2,2’:6’,2’’-terpyridine (mtpy) 19
3.1.2 Syntheses of Metal complexes 19
3.1.2.1 Syntheses of complex Fe(mtpy)2(BF4)2 (1) 19
3.1.2.2 Syntheses of complex Co(mtpy)2(BF4)2 (2) 19
3.1.2.3 Syntheses of complex Fe(mtpy)2(BF4)2 (3) 20
3.1.2.4 Syntheses of complex Co(mtpy)2(BF4)2 (4) 20
3.1.2.5 Syntheses of complex Zn(mtpy)2(ClO4)2 (5) 20
3.1.2.6 Syntheses of complex Fe(mtpy)2(BF4)2•(CH3CN) (6) 20
3.1.2.7 Syntheses of complex Co(mtpy)2((BF4)2•(CH3CN) (7) 20
3.1.2.8 Syntheses of complex Fe(mtpy)(NCS)2 (8) 21
3.1.2.9 Syntheses of complex Co(mtpy)(NCS)2 (9) 21
3.1.2.10 Syntheses of complex Fe(mtpy)2•(NCS)2•(CH3CN) (10) 21
Chapter 4 RESULTS AND DISCUSSION 22
4.1 Characterization of ligand mtpy 22
4.1.1 NMR spectrum of ligand mtpy 22
4.1.2 FTIR spectrum of ligand mtpy 23
4.1.3 Single crystal structure of mtpy 23
4.1.4 UV-Vis spectrum of mtpy 26
4.1.5 Liquid state photoluminescence spectrum of mtpy 27
4.1.6 Solid state Photoluminescence spectrum of mtpy 29
4.2 The - interaction of ligands 30
4.2.1 The calculation - interaction of ligands 30
4.3 Calculation of UV-Vis and PL spectrum for ligands 32
4.3.1 UV-Vis calculation in CH2Cl2 solvent 32
4.4 Characterization of complex Zn(mtpy)2(ClO4)2 (5) 36
4.4.1 FTIR of complex 5 36
4.4.2 Single crystal of complex 5 37
4.4.3 Solid state UV-Vis and PL of complex 5 40
4.4.4 Liquid state UV-Vis and PL of complex 5 41
4.5 Calculation of ligands and complexes quantum yield 42
4.5.1 Relative quantum yield analysis 42
4.5.2 Solid state of quantum yield 44
4.6 Characterization of Fe(mtpy)2(BF4)2 (1) 45
4.6.1 FTIR of Fe(mtpy)2(BF4)2 (1) 45
4.6.2 Indexing of complex Fe(mtpy)2(BF4)2 (1) 46
4.7 Characterization of complex Co(mtpy)2(BF4)2 (2) 47
4.7.1 FTIR of complex Co(mtpy)2(BF4)2 (2) 47
4.7.2 Indexing of complex Co(mtpy)2(BF4)2 (2) 48
4.7.3 SQUID measurement for Co(mtpy)2(BF4)2 (2) 49
4.8 The single crystal of complex Fe(mtpy)2(BF4)2 (3) and Co(mtpy)2(BF4)2 (4) 50
4.8.1 Single crystal of complex 3 50
4.8.2 Single crystal of Co(mtpy)2(BF4)2 (4) 53
4.9 Single crystal of Fe(mtpy)2(BF4)2•(CH3CN) (6) and Co(mtpy)2(BF4)2•(CH3CN) (7) 55
4.9.1 Single crystal of Fe(mtpy)2(BF4)2•(CH3CN) (6) 55
4.9.2 Single crystal of Co(mtpy)2(BF4)2•(CH3CN) (7) 57
4.10 Characterization of Fe(mtpy)(NCS)2 (8) 59
4.10.1 FTIR spectrum of complex 8 59
4.10.2 Indexing of Fe(mtpy)(NCS)2 (8) 59
4.10.3 S K-edge XAS of complex Fe(mtpy)(NCS)2 (8) 60
4.10.4 O K-edge XAS of complex Fe(mtpy)(NCS)2 (8) 61
4.11 Characterization of Co(mtpy)(NCS)2 (9) 62
4.11.1 FTIR spectrum of complex 9 62
4.11.2 Indexing of Co(mtpy)(NCS)2 (9) 63
4.11.3 S K-edge of Co(mtpy)(NCS)2 (9) 64
4.12 Single crystal of Fe(mtpy)2•(NCS)2•(CH3CN) (10) 66
4.13 The bonding distances comparison of Co(ftpy)2(BF4)2, Co(mtpy)2(BF4)2, and Co(mtpy)2(BF4)2•(CH3CN) 69
Chapter 5 SUMMARY AND FUTURE PERSPECTIVE 70
REFFRENCES 72
APPENDIX 76
Complexes indexing for systematic absences 76
Fe(mtpy)2(BF4)2 (1) Space group is P21/n 76
Co(mtpy)2(BF4)2 (2) Space group is P21/n 78
Fe(mtpy)2(NCS)2 (8) Space group is P21/n 81
Co(mtpy)2(NCS)2 (9) Space group is P21/n 84
Table A1. List of material 88

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