Part I. Synthesis and Molecular Assemblies of d10 Metal Complexes Bearing 9, 10-Disubstituted Anthracene Ligand Part II. Synthesis and Spectroscopic Studies of Heterobimetallic Platinum(II)-acetylide and Platinum(0)-acetylene Complexes ZHANG KE (B.Sci., Beijing University) A THESIS SUBMITTED FOR THE DEGREE OF PHD OF SCIENCE DEPARTMENT OF CHEMISTRY NATIONAL UNIVERSITY OF SINGAPORE 2006 Acknowledgement This thesis is a result of four years work whereby I have been accompanied and supported by many people. It is a pleasant aspect that I have now the opportunity to express my gratitude for all of them. The first person I would like to thank is my supervisor Dr. Yip, Hon Kay John, who has provided me continuous care and guidance on my research work. His overly enthusiasm on research has made a deep impression on me. Not only the knowledge but also the scientific attitude, which I learned from him, will be great fortune to me in my future career and life. I would like to thank the colleagues in our research group: Mr. Lin Ronger, Dr. Wu Jianguo, Mr. Hu Jian, Dr. Xu Huan and Miss. Wang Yuanyuan. From all of them, I have received great help on my experiments and valuable discussion. My special thanks are given to Miss. Tan Geok Kheng and Prof. Koh Lip Lin for their assistance on crystal structure analysis. I appreciate Dr. Wang Kwok-Yin for his assistance on electrochemical measurements of a series of my complexes. I also thank Dr. Leong Weng Kee for his providing me some of the starting materials. It is my pleasure to give my thanks to all the staffs in the Chemical, Molecular and Materials Analysis Centre (CMMAC) at the Department of Chemistry in National University of Singapore for their assistance on characterization of my compounds. I want to show my acknowledgement to the National University of Singapore for the scholarship to pursue my Ph. D. degree. Finally, I am indebted to my beloved parents and wife. Their infinite encouragement endowed me with confidence to complete this thesis. i Table of Contents Acknowledgements……………………………………………………………………… i Table of Contents………………………………………………………………… .ii List of Abbreviations…………………………………………………………………….v Summary…………………………………………………………………………………vi Part I. Synthesis and Molecular Assemblies of d10 Metal Complexes Bearing 9, 10-Disubstituted Anthracene Ligand Chapter 1. Roles of Anthracene Unit in Inorganic Chemistry 1.1 A luminophore for chemosensors…………………………………………………… 1.2 -coordinating to metal cations……………………………………………………… 1.3 A bridging unit in crystal engineering……………………………………………… .4 1.4 Phosphorus-substituted anthracenes………………………………………………… 1.5 Use of the anthracene unit in our group……………………………………………….6 1.6 Objectives…………………………………………………………………………… Chapter 2. Molecular Assemblies of AuI Complexes with 9, 10Bis(diphenylphosphino)anthracene Ligand 2.1 Introduction………………………………………………………………………… 11 2.1.1 Au-Au interaction…………………………………………………………… .11 2.1.2 - interaction………………………………………………………………….13 2.1.3 Objectives…………………………………………………………………… .15 2.2 Results and discussion……………………………………………………………….16 2.2.1 Synthesis and characterization…………………………………………………16 2.2.2 Crystal structures………………………………………………………………18 2.2.3 Electronic absorption and emission spectroscopy…………………………… 34 2.3 Conclusions………………………………………………………………………… 41 2.4 Experimental section…………………………………………………………………42 Chapter 3. First Examples of AuI-X-AgI Halonium Cations ii 3.1 Introduction…………………………………………………………………………. 45 3.2 Objectives……………………………………………………………………………46 3.3 Results and discussion……………………………………………………………….47 3.4 Conclusions………………………………………………………………………… 51 3.5 Experimental section…………………………………………………………………52 Chapter 4. Systhesis, Structures and Electronic Spectroscopy of d10 Metal Complexes with 9, 10-Anthracenedithiol Ligand 4.1 Introduction………………………………………………………………………… 55 4.2 Objectives……………………………………………………………………………56 4.3 Results and discussion……………………………………………………………….57 4.3.1 Synthesis and crystal structures……………………………………………… 57 4.3.2 Electronic absorption and emission spectroscopy…………………………… 65 4.4 Conclusions………………………………………………………………………… 68 4.5 Experimetal section………………………………………………………………… 69 Part II. Synthesis and Spectroscopic Studies of Heterobimetallic Platinum(II)acetylide and Platinum(0)-acetylene Complexes Chapter 5. Introduction on Metal Acetylide/Acetylene Complexes of Electrochemical and Photophysical Properties 5.1 Mixed-valence complexes………………………………………………………… .75 5.2 C C based bridges in mediating electronic communication……………………… .79 5.3 Photophysical properties…………………………………………………………… 82 5.4 Objectives……………………………………………………………………………84 Chapter 6. Synthesis and Electrochemical Studies of Heterobimetallic Platinum(II) Ferrocenylacetylide Complexes 6.1 Introduction………………………………………………………………………… 89 6.2 Results and discussion……………………………………………………………….89 iii 6.2.1 Synthesis and characterization…………………………………………………90 6.2.2 Crystal structures………………………………………………………………95 6.2.3 Electronic absorption spectroscopy………………………………………… 106 6.2.4 Electrochemistry…………………………………………………………… .109 6.3 Conclusions…………………………………………………………………………117 6.4 Experimental section……………………………………………………………… 118 Chapter 7. Synthesis and Photophysical Studies of a Series of Platinum(0)-acetylene Complexes 7.1 Introduction…………………………………………………………………………126 7.2 Results and discussion…………………………………………………………… .128 7.2.1 Synthesis and characterization……………………………………………… 128 7.2.2 Crystal structures…………………………………………………………… 130 7.2.3 Electronic spectroscopy………………………………………………………134 7.3 Conclusions…………………………………………………………………………144 7.4 Experimental section……………………………………………………………… 145 Physical Measurements .…………………………………………………………… 149 References…………………………………………………………………………… .153 Publications……………………………………………………………………………175 Appendices…………………………………………………………………………….176 iv List of Abbreviations AnSSAn di-9-anthryl disulfide bipy 4, 4’-bipyridine t Bu2bpy 4, -di-tert-butyl-2, -bipyridine COD 1, 5-cyclooctadiene dcypm bis(dicyclohexylphosphino)methane dmpm 1, 2-bis(dimethylphosphino)methane dppf 1, -bis(diphenylphosphino)ferrocene dppm bis(diphenylphosphino)methane dppp 1, 3-bis(diphenylphosphino)propane Fc ferrocenyl HOMO highest occupied molecular obital H2SAnS 9, 10-anthracenedithiol LMCT ligand-metal charge-transfer LUMO lowest unoccupied molecular obital MLCT metal-ligand charge-transfer NS22- 1, 8-naphthalenedithiolate NLO nonlinear optical OTf- triflate anion PAnP 9, 10-bis(diphenylphosphino)anthracene SAnS2- 9, 10-anthracenedithiolate S-tmhd thiolate of 5-mercapto-2,2,6,6-tetramethyl-4-hepten-3-one TBAH tetrabutylammonium hexafluorophosphate v Summary Group 10/11 transition metal complexes are of considerable interest due to their structural diversities and great potential for developing novel materials of molecular scale in various fields such as optical, electronic and medical materials. This thesis consists of two parts of work on the synthesis and characterization of metal complexes of these two groups. The objective of the first part of work was to develop d10 complexes of interesting structural properties by utilizing metal-metal and/or - interactions for assembling molecules. In the second part, to search for novel molecules of electronic and optical properties, spectroscopy of a series of heterobimetallic platinum(II)-acetylide and platinum(0)-acetylene complexes were studied. In the first part of work, AuI diphosphine complexes formulated as ( -PAnP)(AuX)2 (PAnP: 9, 10-bis-diphenylphosphinoanthracene; X: Cl(1), Br(2), I(3), NO3(4), -C CPh(5), -C CC14H9(6)) were prepared and structurally characterized by X-ray diffraction analysis. Molecules in crystals of 1·CH2Cl2, 3·CH2Cl2, 4·0.5Et2O and 5·THF form dimers via both Au-Au and - interactions (between anthracene units), whereas those in 1·0.5Et2O, 2·Et2O and 2·2CH2Cl2 dimerize only through the latter. Intermolecular edge-to-face interactions were observed in 6·0.75CH2Cl2 to dominate over Au-Au interactions, faceto-face and off-set - interactions. All these complexes show strong ligand-centered fluorescence. Slow diffusion of THF solution of AgSbF6 into CH2Cl2 solution of complexes or gives rise to the formation of novel AuI-X-AgI halonium complexes ({[( -PAnP)(AuCl)2]2Ag}+SbF6- (7) or {[( -PAnP)(AuBr)2]2Ag}+SbF6- (8)), structures of which are stabilized by the collective actions of Ag-X and Au-Ag and - interactions. Reaction of 9, 10-anthracenedithiol H2SAnS with different starting materials ([Cu2( - vi dppm)2(CH3CN)2](PF6)2, [Ag2( -dppm)2](ClO4)2 and PPh3AuCl) (dppm: bis- diphenylphosphinomethane) formed three different d10 metal thiolates: [(Cu2( 2dppm)2)2( 2- 2-SAnS)](PF6)2 (9), [(Ag2( 2-dppm)2)2( 2- 2-SAnS)](ClO4)2 (10) and (Ph3PAu)2( -SAnS-SAnS) (11). The anthracene unit plays a key role in stabilizing the structures of these complexes by forming - interactions. The ligand H2SAnS and complexes 9-11 all show intense ligand-centered emissions ( * and n *) in degassed solution. In the second part of work, PtII-acetylide complexes formulated as trans-(Fc-C C)2Pt( -dppm)2M(L) (Fc: ferrocenyl; M(L): nothing(12), Au(ClO4)(13), Ag(NO3)(14), Cu(PF6)(15), Hg(Cl2)(16), Rh(CO)(PF6)(17), W(CO)3(18), Mo(CO)3(19)) were synthesized. Crystal structure results show the presence of intramolecular Pt M interaction in 13-19. The heterogeneous metal atom M also coordinates to one or both carbon atoms of one of the C C bonds attached on Pt in 15, 17, 18 and 19. UV-visible spectroscopic studies show that metal-metal interactions exist in solution for 13-17. The voltammetric data show that while the electronic communications in 13 and 14 are as poor as that in mononuclear complex trans-Pt(C CFc)2(PPh2Me)2 (20), Pt Hg interaction in 16 can enhance electronic communication along the C C-Pt-C C bridge. In addition, electronic spectroscopic properties of a series of platinum(0)-acetylene complexes (Pt(PPh3)2(PhC2Ph) (21), Pt(dppp)(PhC2Ph) (22), Pt(PPh3)2(PhC4Ph) (23), Pt(dppp)(PhC4Ph) (24), (Pt(dppp))2(PhC4Ph) (25), Pt(dppp)(CH3C4CH3) (26) and (Pt(dppp))2(CH3C4CH3) (27)) (dppp: 1, 3-bis(diphenylphino)propane) were investigated in the second part of work. All these complexes show interesting MLCT phosphorescence in both solid state and frozen solution. vii Part I. Synthesis and Molecular Assemblies of d10 Metal Complexes Bearing 9, 10-Disubstituted Anthracene Ligand Chapter Roles of Anthracene Unit in Inorganic Chemistry A-82. 1H-NMR spectrum of complex 21 in CDCl3 at room temperature A-83. 31P{1H}-NMR spectrum of complex 21 in CDCl3 at room temperature 223 A-84. 1H-NMR spectrum of complex 22 in CDCl3 at room temperature A-85. 31P{1H}-NMR spectrum of complex 22 in CDCl3 at room temperature 224 7.72 7.68 7.64 7.60 7.56 7.52 7.48 7.44 7.40 7.36 7.32 7.28 7.24 7.20 7.16 7.12 7.08 7.04 7.00 6.96 6.92 6.8800 6.9496 6.9442 6.9389 6.9268 6.9014 6.9670 6.9911 7.1061 7.0994 7.0887 7.0794 7.0606 7.0553 7.1583 7.1356 7.1302 7.1837 7.2198 7.2118 7.3911 7.3777 7.3550 7.3510 7.4366 7.4138 7.4085 7.76 6.88 6.84 6.80 6.76 6.72 6.68 6.64 (ppm) 45 44 43 42 41 40 39 38 37 36 35 34 33 32 31 30 29 28 27 26 12.4341 12.2144 11.7748 11.5864 26.6259 26.4375 26.2805 26.0921 40.2211 40.0327 41.4142 41.1944 A-86. 1H-NMR spectrum of complex 23 in CDCl3 at room temperature 25 24 23 22 21 20 19 18 17 16 15 14 13 12 11 10 (ppm) A-87. 31P{1H}-NMR spectrum of complex 23 in CDCl3 at room temperature 225 8.4 8.2 8.0 7.8 7.6 7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 2.8 2.6 2.1064 2.0904 2.0489 2.0328 2.0154 1.9606 1.9419 2.0000 2.6081 2.5747 4.0521 30.854 7.0339 7.0285 7.0192 7.0098 7.3389 7.3135 7.2948 7.2881 7.2800 7.7978 7.7938 7.7871 7.7791 7.7751 7.7684 7.7617 7.7563 7.7510 7.7430 7.7323 7.7242 Integral 8.6 2.4 2.2 2.0 1.8 (ppm) 22 21 20 19 18 17 16 15 14 13 12 11 10 -8.8535 -8.9791 -9.4186 -9.5756 3.2660 3.1404 4.9301 4.8045 15.9821 15.8251 18.7137 18.5881 A-88. 1H-NMR spectrum of complex 24 in CDCl3 at room temperature -1 -2 -3 -4 -5 -6 -7 -8 -9 -10 -11 -12 -13 -14 (ppm) A-89. 31P{1H}-NMR spectrum of complex 24 in CDCl3 at room temperature 226 7.8 7.6 7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 1.6785 4.0000 2.2404 8.0506 7.0206 7.0073 7.0033 6.9992 6.9029 6.8949 6.8748 6.8494 6.8293 6.8093 6.7812 19.715 8.0 29.645 7.9090 7.9010 7.8863 7.8742 7.8662 7.8046 7.7766 7.6789 7.6722 7.6521 7.6481 Integral 8.2 2.0 1.8 1.6 (ppm) 24 22 20 18 -8.9178 -9.1376 -9.6400 -9.8597 4.3006 4.0494 3.8296 17.8958 17.6760 17.2365 17.0481 A-90. 1H-NMR spectrum of complex 25 in C6D6 at room temperature 16 14 12 10 -2 -4 -6 -8 -10 -12 -14 (ppm) A-91. 31P{1H}-NMR spectrum of complex 25 in C6D6 at room temperature 227 22 20 18 6.5 16 6.0 14 5.5 12 5.0 10 -5.1635 -5.4195 -5.4683 -5.7244 7.0 7.4079 7.1641 7.5 8.6029 8.3468 20.2476 19.9915 24 22.4302 22.1742 8.0 (ppm) 4.5 4.0 3.5 3.0 2.5 -2 -4 2.0 -6 1.5 A-92. 1H-NMR spectrum of complex 26 in C6D6 at room temperature (ppm) -8 A-93. 31P{1H}-NMR spectrum of complex 26 in C6D6 at room temperature 228 2.0000 3.0119 4.0126 3.0009 12.205 3.9628 3.9786 Integral 2.8357 2.8110 2.7700 2.7448 2.7009 2.6812 2.2062 2.1662 2.1405 2.0999 1.9378 1.9257 1.9060 1.8945 1.8720 1.8660 1.6940 1.6200 1.5444 7.0985 7.0777 7.0240 7.0043 6.9999 6.9807 7.9822 7.9543 7.9236 7.7116 7.7056 7.6853 7.6798 7.6502 24 22 8.0 7.5 20 7.0 18 6.5 16 6.0 14 12 5.5 10 -4.7419 -4.8675 8.7277 8.5393 8.3509 21.9461 21.8205 8.5 (ppm) 5.0 4.5 4.0 3.5 3.0 2.5 -2 2.0 A-94. 1H-NMR spectrum of complex 27 in C6D6 at room temperature (ppm) -4 -6 A-95. 31P{1H}-NMR spectrum of complex 27 in C6D6 at room temperature 229 4.0000 7.9166 5.9786 22.076 17.023 Integral 2.5896 2.5735 2.5173 2.5106 2.5026 2.4464 2.4304 2.2618 1.8163 1.7413 1.6691 7.1063 7.0809 7.0568 7.0407 7.0167 6.9765 6.9524 6.9297 8.0281 8.0214 8.0027 7.9987 7.8649 7.8595 7.8368 7.8328 7.8248 7.8087 7.8033 70 Transmittance (%) 60 50 40 2110 30 20 10 2400 2200 2000 1800 1600 1400 1200 1000 800 600 800 600 -1 Wavenumber (cm ) A-96. IR (KBr) spectrum of complex 70 Transmittance (%) 60 50 40 30 2091 20 10 2400 2200 2000 1800 1600 1400 1200 1000 -1 Wavenumber (cm ) A-97. IR (KBr) spectrum of complex 230 Transmittance (%) 70 60 2110 50 40 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-98. IR (KBr) spectrum of complex 12 80 Transmittance (%) 70 2112 60 50 40 30 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-99. IR (KBr) spectrum of complex 13 231 80 Transmittance (%) 70 60 2106 50 40 30 20 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-100. IR (KBr) spectrum of complex 14 80 Transmittance (%) 70 60 2118 2074 50 40 30 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-101. IR (KBr) spectrum of complex 15 232 75 Transmittance (%) 70 65 60 2107 55 50 45 40 35 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-102. IR (KBr) spectrum of complex 16 80 Transmittance (%) 70 60 2026 50 40 30 1967 20 10 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-103. IR (KBr) spectrum of complex 17 233 80 Transmittance (%) 70 60 50 2118 1953 40 30 20 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-104. IR (KBr) spectrum of complex 18 100 Transmittance (%) 90 80 70 2107 1953 60 50 40 30 20 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-105. IR (KBr) spectrum of complex 19 234 Transmittance (%) 70 60 2110 50 40 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-106. IR (KBr) spectrum of complex 20 Transmittance (%) 80 70 1741 60 50 40 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-107. IR (KBr) spectrum of complex 21 235 80 Transmittance (%) 70 60 1748 50 40 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-108. IR (KBr) spectrum of complex 22 80 Transmittance (%) 70 1721 60 2161 50 40 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-109. IR (KBr) spectrum of complex 23 236 70 Transmittance (%) 60 50 40 30 1719 20 10 2160 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-110. IR (KBr) spectrum of complex 24 80 Transmittance (%) 70 60 50 1758 40 30 20 10 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-111. IR (KBr) spectrum of complex 25 237 100 Transmittance (%) 80 2196 60 1749 40 20 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-112. IR (KBr) spectrum of complex 26 100 Transmittance (%) 80 60 1705 40 20 2400 2200 2000 1800 1600 1400 1200 1000 800 600 -1 Wavenumber (cm ) A-113. IR (KBr) spectrum of complex 27 238 [...]... work are given in Chapter 4 SH SH Figure 1.5 Structure of 9, 10- anthracenedithiol (H2SAnS) 9 Chapter 2 Molecular Assemblies of AuI Complexes with 9, 10Bis(diphenylphosphino )anthracene Ligand 10 2.1 Introduction Gold(I) phosphine complexes have received great attention for many years.21-23 Because of the soft acid nature of gold(I), P-donor ligands as soft bases have a strong affinity for gold(I) centers... Therefore, the ligand 9, 10bis(diphenylphosphino )anthracene (PAnP) has been synthesized in our group and utilized as a building block in crystal engineering of d10 metal complexes The preparation of the ligand is shown in Scheme 1.4 Treatment of PAnP with one equivalent of Au I ions Li Br PPh2 2 eq n-BuLi, ether 2 eq Ph2PCl r.t ice bath Li Br PPh2 PAnP Scheme 1.4 Synthesis of the ligand PAnP produced... Bis(diphenylphosphino )anthracene serves as a neutral chelating donor ligand in transition metal chemistry.16 More recently, Kubiak and co-workers has synthesized the ligand {1(9 -anthracene) phosphirane}, and investigated the structural properties of its platinum(II) complexes (Figure 1.1).17 While the molecular structure of complexes A and B are dominated by intramolecular -stacking between the anthracene rings, that of. .. results obtained from the ligand PAnP, we were wondering if displacement of phosphorus with other coordinating element such as sulfur would lead to another interesting ligand Therefore, another objective of the present work was to synthesize a designed ligand 9, 10- anthracenedithiol (H2SAnS, Figure 1.5) and investigate its coordination chemistry with d10 metals Results of this portion of work are given in... intermolecular -stacking between anthracene rings of two adjacent molecules P Cl P Pt CO2Et S CO2Et Pt Cl P S P B A CN CN S P S Pt P P Pt S P S NC NC C Figure 1.1 Structures of three platinum(II) complexes of the ligand {1-(9 -anthracene) phosphirane} 1.5 Use of the anthracene unit in our group 6 However, to our knowledge, the coordination chemistry of diphosphorus-substituted anthracenes at 9- and 10- positions... P(n-Bu)3, HPPh2 or PPh3 Scheme 1.2 A series of -coordination complexes of an anthracenecontaining ligand 1.3 A bridging unit in crystal engineering 4 9, 10- Disubstitued anthracene derivatives are important building blocks in crystal engineering .10 For instance, recently Mirkin and co-workers have used a designed anthracene- containing bidentate ligand to synthesize a metallocyclophane which could trap an... 2.3 Examples of gold(I) macrocycles O CH2 C C Au Au C C H2C O PPh2 Figure 2.4 An example of gold(I) catenane 2.1.2 - interaction Besides metal- metal interactions, the interactions between ligands are another important factor in crystal engineering of late transition metal complexes One of the most common 13 types of ligand interactions is - interaction, which is often observed in compounds bearing large... to tune the electron density of the gold(I) centre which is a key factor in controlling Au-Au separations 2.2 Results and discussion 2.2.1 Synthesis and characterization The synthesis routes for complexes 1 to 6 is shown in Scheme 2.1 Complexes 1 and 2 were prepared by ligand substitution of a strong donor PAnP for a weak donor Me2S, which is commonly used for synthesis of phosphine gold(I) halides... occupancies of 0.5 and 0.5 The 24 (a) (b) (c) Figure 2.12 (a) ORTEP diagram of a monomer of 4·0.5Et2O (the disorder of one of the nitrate groups is shown by bonds of open lines and the dashed-open line indicates the Au-O interaction; for clarity, phenyl rings are in thin line format and all H atoms and solvent molecules are omitted); (b) ORTEP diagram of a dimer of 4·0.5Et2O (for clarity, only half of positions... -PAnP)(AuCl)2 (1) and ( -PAnP)(AuBr)2 (2) show no Au-Au interaction.18b However, the packing of these molecules are not discussed in our previous study In fact, these molecules are packed in dimers via - interaction between neighboring anthracene rings As the intermolecular Au-Au seperation of phosphinegold(I) complexes depends on the nature of the ancillary ligand, 20 changing the ancillary ligand of ( -PAnP)(AuX)2 . Part I. Synthesis and Molecular Assemblies of d 10 Metal Complexes Bearing 9, 10- Disubstituted Anthracene Ligand Part II. Synthesis and Spectroscopic Studies of Heterobimetallic Platinum(II)-acetylide. Summary…………………………………………………………………………………vi Part I. Synthesis and Molecular Assemblies of d 10 Metal Complexes Bearing 9, 10- Disubstituted Anthracene Ligand Chapter 1. Roles of Anthracene Unit in Inorganic Chemistry. both solid state and frozen solution. 1 Part I. Synthesis and Molecular Assemblies of d 10 Metal Complexes Bearing 9, 10- Disubstituted Anthracene Ligand 2