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Organic Sulfenyl Chlorides As Precursors for the Modification of Gold Surfaces

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Organic Sulfenyl Chlorides As Precursors for the Modification of Gold Surfaces Organic Sulfenyl Chlorides as Precursors for the Modification of Gold Surfaces by Hamida Sultan Muhammad A Thesis presented to The University of Guelph In partial fulfilment of requirements for the degree of Doctor of Philosophy in Chemistry Guelph, Ontario, Canada © Hamida Sultan Muhammad, May, 2013 ABSTRACT ORGANIC SULFENYL CHLORIDES AS PRECURSORS FOR THE MODIFICATION OF GOLD SURFACES Hamida Sultan Muhammad Advisor: University of Guelph, 2013 Professor A. Houmam Self-assembled monolayers (SAMs) of organosulfur precursors on gold have been extensively used since they offer a wide range of technological applications such as corrosion inhibition, lubrication, adhesion promotion/inhibition, nanofabrication, chemical and biosensors, catalysis, and molecular electronics. Furthermore, the electronic and optical properties of aromatic SAMs make them a potential candidate for molecular electronics. However, these practical applications are limited by the short-range ordering, low packing density, irreproducibility, and inferior quality of SAMs, which are more critical for aromatic SAMs. Therefore, the discovery of alternative precursors is essential. This thesis reports for the first time, the use of organic sulfenyl chlorides as precursors for the modification of gold surfaces. These precursors may help to overcome some practical limitations of the traditional organosulfur precursors. The modification is done in a non-aqueous medium. Characterization of the modified surfaces is performed by X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and scanning tunnelling microscopy (STM). Through the use of 4-nitrophenyl sulfenyl chloride, evidence for the formation of well-ordered aromatic SAMs formation on gold is provided. XPS data shows that the modification involves the scission of the S-Cl bond. PM-IRRAS studies further indicate that the adsorbed molecules are nearly vertically oriented on the surface. Both short and long-range well- ordered aromatic SAMs (a 4 x √3 rectangular and √3 x √3 hexagonal unit cells) are obtained from the STM images using two different modification conditions. This molecular density is usually only observed for aliphatic SAMs using the traditional precursors. Along with the main hexagonal lattice, the reversible distinct superstructures including hexagons, partial hexagons, parallelograms, and zigzags resulting from specific arrangements of adsorbed molecules provide submolecular details. This is the first direct experimental example, where the STM has shown its effectiveness to provide physical structure information of standing-up aromatic SAMs at room temperature. This work also provides some insight into a heavily debated issue regarding the origin of the various features and contrasts obtained in STM images of SAMs. The use of 2-nitrophenyl sulfenyl chloride and 2,4-dinitrophenyl sulfenyl chloride for the formation of aromatic SAMs on Au provides some insight regarding the modification extent and the effect of a nitro substituent (at ortho position ) on the quality of nitrophenyl thiolate SAMs on gold. XPS, PM-IRRAS, electrochemistry and STM provide evidence for the formation of less ordered, low density and less stable SAMs that may decompose to sulfur at longer modification times. The efficient deposition of sulfur on gold is observed using a series of substituted methane sulfenyl chlorides (triphenylmethane sulfenyl chloride, trichloromethane sulfenyl chloride and chlorocarbonyl sulfenyl chloride). The XPS, STM and electrochemical data show the formation of high density sulfur phases. These include rhombus, rectangular, and zig-zag sulfur structures. A mechanism is suggested involving the cleavage of the S-Cl bond and the ejection of the molecular backbone. This study also suggests that substituted methane sulfenyl chlorides do not form long-range ordered SAMs. Acknowledgements First off all, I would like to thank my supervisor, Dr. Abdelaziz Houmam for accepting me into his research group and for all his help and guidance while pursuing my PhD degree. His ideas and patience made the experience an enjoyable one. Also I would like to thank my advisory committee members, Dr. Daniel F. Thomas and Dr. Wojciech Gabryelski for their helpful suggestions, and my examination committee members Dr. Tong Leung, Dr. Paul Rowntree and Dr. Peter Kruse. I would also like to thank Dr. Mario Monteiro for agreeing to chair my thesis defense. Lab members, former and current, I would like to thank, Dr. Emad Hamed, Dr. Md. Golam Moula, Dr. Kallum M. Koczkur, Nusrat Serhat Un, Yimeng He and Goli Pourmand, all of who made my time in the Houmam lab a lot of fun. A special thank you goes to Dr. Daniel F. Thomas, Dr. Kallum M. Koczkur and Ryan Seenath for helping me editing my PhD thesis. I would also like to appreciate Dr. Kallum M. Koczkur for conducting XPS experiments and his help during other lab work. I would like to thank Dr. Grzegorz Szymanski for his help and assistance in working on Raman spectrometer and ellipsometer and Dr. Md.Golam Moula for his advices on the use of STM, vapour deposition system and electrochemical etching of STM tips. I am also grateful to Dr. Paul Rowntree, Stuart Read and Ann Vandergust for their help in keeping Midas operational. Also, to Dr. Md. Golam Moula, Ann Vandergust, Dr. Annia H. Kycia and Jay Leitch for their help in performing surface IR experiments and all of my neighbours in the MacNaughton building and Science Complex. Finally, I would like to thank my parents and siblings for their continuous support and encouragement. iv Dedicated to My Parents and Siblings v Table of Contents Page no. i) Acknowledgements iv ii) Dedication v iii) List of Tables x iv) List of Schemes x v) List of Charts xi vi) List of Figures xii vii) List of Abbreviations xxiv viii) List of Symbols xxviii Preamble 1 Chapter I: Introduction and Background Information I-1 General Background 3 I-2 Common Methodologies used for Surface Modification 5 I-3 Self-Assembled Monolayers (SAMs) 7 I-4 Organosulfur SAMs on Au 11 I-4a Building Blocks of Organosulfur SAMs on Au 11 I-4b Significance of Organosulfur SAMs on Au 14 I-4c Thermodynamics and Kinetics of Formation of Organosulfur 16 SAMs on Au I-4d Mechanism of Formation of Organosulfur SAMs on Au 20 I-4e Modification Conditions for Organosulfur SAMs on Au 24 I-4f Structures of Organosulfur SAMs on Au 27 I-4g Debated Au-S Interface 30 vi I-4h The Quality of Organosulfur SAMs 45 I-4i Aromatic Organosulfur SAMs on Au 49 I-4j Interpretation of STM Images of Organosulfur SAMs 54 I-5 Motivation of the Research 59 I-6 Scope of Thesis 62 Chapter II: Experimental Part II-1 Chemicals 65 II-2 Preparation of Au(111) Substrates 65 II-3 Modification of the Gold Surfaces 66 II-4 Characterization of the Modified Surfaces 67 II-4a Scanning Tunnelling Microscopy 67 II-4b X-ray Photoelectron Spectroscopy 73 II-4c Polarization Modulation Infrared Reflection Absorption 78 Spectroscopy II-4d Cyclic Voltammetry 85 Chapter III. 4-Nitrophenyl Sulfenyl Chloride as a New Precursor for the Formation of Aromatic SAMs on Gold Sulfaces III-1 Introduction 91 III-2 Modification under Condition 1 93 III-2a Modification Procedure 93 III-2b Results and Discussion 94 III-3 Modification under Condition 2 105 vii III-3a Modification Procedure 105 III-3b Results and Discussion 106 III-4 Proposed Mechanism of SAM Formation 125 III-5 Summary and Conclusions 126 Chapter IV. The Effect of Substituent(s) Position(s) on SAMs of Nitro Aromatic Sulfenyl Chlorides on Gold Surfaces IV-1 Introduction 128 IV-2 Modification using Compound 2 130 IV-2a Modification Procedure 130 IV-2b Results and Discussion 130 IV-3 Modification using Compound 3 140 IV-3a Modification Procedure 140 IV-3b Results and Discussion 140 IV-4 Comparison of Compounds 1-3 149 IV-5 Proposed Adsorption Mechanism for Compounds 2 and 3 153 IV-6 Summary and Conclusions 153 Chapter V. Substituted Methane Sulfenyl Chlorides as Precursors for the Modification of Gold Surfaces V-1 Introduction 155 V-2 Modification Procedure 156 V-3 Results and Discussion 156 V-3a XPS Characterization 156 viii V-3b Stripping Voltammetry 160 V-3c STM imaging 170 V-4 Proposed Mechanism of Sulfur Deposition for Compounds 4-6 on Au 178 V-5 Summary and Conclusions 180 Chapter VI: Summary and Future Work VI-1 Summary 182 VI-2 Future Work 186 Chapter VII: References 190 Appendix A: Copyright Permissions 227 ix List of Tables Chapter I: Table 1-1. Energies of adsorption (kcal/mol) for methanethiol SAM on Au(111) at different adsorption sites. Table 1-2. Bond dissociation energies (S-Y bonds) and reduction potentials of compounds 4- RPhSY. List of Schemes Chapter III: Scheme 3-1. Global reduction reaction of arene sulfenyl chlorides and arene thiocyanates. Scheme 3-2. Proposed deposition mechanism. Chapter IV: Scheme 4-1. Proposed deposition mechanism. Chapter V: Scheme 5-1. Proposed deposition mechanism for compound 4-6 on Au. Chapter VI: Scheme 6-1. Proposed reactions of the terminal nitro group of the 4-nitrophenyl thiolate SAM on Au in an electrochemical environment. Scheme 6-2. Proposed reactions of the terminal group of the 4- phenyl thiolate SAM on Au in an electrochemical environment using SECM tip. x Scheme 6-3. Scheme for the synthesis of mixed-ligand CdS nanoclusters containing 1 mol % of 4-(4-Nitrophenylazo) thiophenol ligand. List of Charts Chapter III: Chart 3-1. Structure of 4-nitrophenyl sulfenyl chloride (1). Chapter IV: Chart 4-1. Structures of 2-nitrophenyl sulfenyl chloride (2) and 2,4-dinitrophenyl sulfenyl chloride (3). Chapter V: Chart 5-1. Structures of compounds 4-6. xi List of Figures Chapter I: Figure 1-1. Illustrations of Langmuir, Langmuir-Blodgett and Langmuir-Schaefer films deposition methods. Figure 1-2. Schematics showing (a) a trichlorosilane SAM on SiO2, (b) an alkanethiol SAM on Au, (c) a fatty acid SAM on Al2O3, and (d) a fatty acid SAM on Ag2O.
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