Synthesis and characterization of group 11, 12 and 13 metal selenocarboxylates potential single molecular precursors for metal selenide nanocrystals 1

SYNTHESIS AND CHARACTERIZATION OF GROUP 11, 12 AND 13 METAL SELENOCARBOXYLATES: POTENTIAL SINGLE MOLECULAR PRECURSORS FOR METAL SELENIDE NANOCRYSTALS NG MENG TACK (B. Sc (Hons) NUS) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY DEPARTMENT OF CHEMISTRY NATIONAL UNIVERSITY OF SINGAPORE 2006 I Declaration This work described in this thesis was carried at the Department of Chemistry, National University of Singapore from 21st July 2002 to 21st July 2006 under the supervision of Associate Professor Jagadese J. Vittal. All the work described herein is my own, unless stated to the contrary, and it has not been submitted previously for a degree at this or any other university. Ng Meng Tack November 2006 II ACKNOWLEDGEMENTS I would like to express my deepest gratitude to my supervisor, Associate Professor Jagadese J. Vittal, for his moral and intellectual support during the course of this project. With his guidance, I have really learned a lot from the enlightening discussions during the training period. I would like to thank Dr. Chris Boothroyd from Institite of Materials Research and Engineering (IMRE) for his valuable discussion on the phase properties of Ag2Se and AgInSe2 NPs. Here, I would like to give special mention to my colleagues for their effort in setting up a comfortable and causative working space in the lab for me. To my friends Sin Yee, Li Hui, Doris, Tze Wee, Wee Leng and Danny: Sincere thanks for their willingness to share with me. Truly, I am also indebted to my beloved parents for their invaluable moral support and patient confidence in me. I greatly appreciate the scholarship from the National University of Singapore during my studies. Last but no least, I would like to extend my appreciation to staff from the TG lab, NMR lab, Microanalytical, TEM and IR lab. Your help has been invaluable. III Table of Contents Acknowledgements Table of Contents I Abbreviations and Symbols VIII Summary XI List of Compounds Synthesized XIV List of Figures XVIII List of Tables and Schemes XXIII List of Publications XXV Chapter 1. Introduction to the Chemistry of Monochalcogenocarboxylate 1.1 General Introduction 1.2 Group 11 Metal Thio- and Selenocarboxylates 1.2.1 Copper Thio- and Selenocarboxylates 1.2.2 Silver Thiocarboxylates 1.2.3 Dppm 1.2.4 1.3 Compounds of Copper and Silver Thiocarboxylates Homoleptic Copper and Silver Thiocarboxylates Group 12 Metal Thio- and Selenocarboxylates 1.3.1 Neutral Group 12 Metal Thio- and Selenocarboxylates Containing N-donor Ligands 1.4 11 Other Metal Thiocarboxylates 1.4.1 12 Group 13 Metalloligands Anion, [M(SC{O}Ph)4]– (M = Ga3+, In3+) 12 I 1.4.2 1.5 Heterobimetallic Metal Thiocarboxylates 13 Single-Source Precursors for Metal Sulfides and Selenides 14 1.5.1 16 Thin Films 1.5.1.1 (Et3NH)[In(SC{O}Ph)4]·H2O, a Precursor for CuInS2 Thin Film 1.5.2 1.6 Chapter 16 Nanoparticles 17 1.5.2.1 Cu2-xSe and Ag2S NPs 17 1.5.2.2 PbS and CdS NPs 18 1.5.2.3 AgInS2 NPs 20 Aim and Scope of Part I of This Thesis 2. Synthesis, Structure and 21 Solution NMR Properties of (Ph4P)[M(SeC{O}Tol)3], M = Zn, Cd and Hg 2.1 Introduction 22 2.2 Results and Discussion 23 2.2.1 Metal NMR Spectra 23 2.2.2 ESI-MS Studies 27 2.2.3 Structures of [M(SeC{O}Tol)3]– (M = Zn – Hg) 29 2.3 Summary 34 2.4 Experimental 34 2.4.1 NMR Studies 34 2.4.2 ESI-MS Studies 35 2.4.3 Syntheses 36 II Chapter 3. Hetero-bimetallic and Polymeric Selenocarboxylates Derived from [M(Se(C{O}Ph)4]– (M = Ga and In) as Molecular Precursors for Ternary Selenides 3.1 Introduction 39 3.2 Results and Discussion 40 3.2.1 Structures of Hetero Bi-metallic and Polymeric Selenocarboxylates 41 3.2.1.1 Structure of (Et3NH)[In(SeC{O}Ph)4]·H2O 43 3.2.1.2 Structures of [K(MeCN)2{M(SeC{O}Ph)4}] 44 3.2.1.3 Structures of [(Ph3P)2M′In(SeC{O}Ph)4]·CH2Cl2 3.2.2 46 Thermogravimetry and Pyrolysis Experiments 49 3.3 Summary 55 3.4 Experimental 55 Chapter 4. Synthesis, Structure and Thermal Properties of [(Ph3P)3Ag2(SeC{O}Ph)2] 4.1 Introduction 61 4.2 Results and Discussion 62 4.2.1 4.2.2 Structure of [(Ph3P)3Ag2(SeC{O}Ph)2] and [(Ph3P)Ag(SeC{O}Ph)]4 63 Thermogravimetry and Pyrolysis Experiments 66 4.3 Summary 68 4.4 Experimental 68 References of Part I of the Thesis 70 III Chapter 5. Introduction to Nanoparticles 5.1 General Introduction 78 5.2 Applications of NPs 80 5.2.1 Luminescence 80 5.2.2 Biological Labeling 81 5.2.3 Light Emitting Diodes 83 5.2.4 Laser 83 5.2.5 Solar Cell 84 5.2.6 Sensing Applications 85 5.3 5.4 Syntheses of Nanomaterials 86 5.3.1 Coprecipitation Synthesis 87 5.3.2 Microemulsion Synthesis 88 5.3.3 Hydrothermal/Solvothermal Synthesis 89 5.3.4 Surfactant-controlled Growth in a Hot Organic Solvent(s) 91 5.3.4.1 95 Single Molecular Precursor Approach Aim and Scope of Part II of This Thesis Chapter 6. 97 Shape and Size Control of Ag2Se NCs from Single Precursor [(Ph3P)3Ag2(SeC{O}Ph)2] 6.1 Introduction 98 6.2 Results and Discussion 99 6.2.1 Formation of Ag2Se NCs from [(Ph3P)3Ag2(SeC{O}Ph)2] 99 6.2.2 Morphology and Characterization of the Ag2Se NCs 101 6.2.3 Growth Mechanism of Ag2Se NPs 105 6.3 Summary 108 IV 6.4 Synthesis and Methodology Chapter 7. Synthesis of Cu2-xSe 108 NPs and Microflakes from [(Ph3P)3Cu2(SeC{O}Ph)2] 7.1 Introduction 110 7.2 Formation and Characterization of Cu2-xSe NPs and Microflakes 111 7.2.1 HDA and TOP as Surfactants 111 7.2.2 DT and TOP as Surfactants 113 7.2.3 Ethylenediamine as Surfactants 116 7.3 Summary 118 7.4 Synthesis and Methodology 118 Chapter 8. Synthesis of ZnSe and CdSe NPs from Neutral Zn(II) and Cd(II) Selenocarboxylates 8.1 Introduction 120 8.2 Results and Discussion 121 8.2.1 Optical Properties of ZnSe NPs 122 8.2.2 Optical Properties of CdSe NPs 125 8.2.3 Structural Characterization of ZnSe and CdSe NPs 129 8.3 Summary 133 8.4 Synthesis and Methodology 134 8.4.1 8.4.2 Synthesis of [Cd(SeC{O}Ph)2] and [Zn(SeC{O}Tol)2]·(H2O) 134 Synthesis of ZnSe and CdSe NPs 135 V Chapter 9. One-Pot Synthesis of New Orthorhombic Phase AgInSe2 NRs 9.1 Introduction 136 9.2 Structural Characterization of AgInSe2 NPs 137 9.3 Crystal Structure Characterization of AgInSe2 NRs 141 9.4 NLO Properties of AgInSe2 NRs 146 9.5 Summary 147 9.6 Synthesis and Methodology 147 Chapter 10. Synthesis of CuInSe2 NPs 10.1 Introduction 149 10.2 Results and Discussion 150 10.2.1 CuInSe2 NPs Synthesized from OA and DT Solvents 150 10.2.2 CuInSe2 NPs Synthesized from DT and TOPO Solvents 153 10.3 Summary 156 10.4 Synthesis and Methodology 157 References of Part II of the Thesis 158 Chapter 11. Summary, Highlight and Possible Extension for Future Work 11.1 Significant of Current Study 170 11.2 Suggestion for Future Work 174 Chapter 12. Experimental 12.1 General 12.1.1 12.2 177 Preparation of Na2Se and K2Se 178 Elemental Analysis 178 VI 12.3 Infrared Spectroscopy 179 12.4 NMR Spectroscopy 179 12.5 ESI-MS 179 12.6 TGA 179 12.7 UV-vis Spectroscopy 179 12.8 Photoluminescence Spectroscopy 179 12.9 X-ray Powder Diffraction 180 12.10 Single Crystal X-ray Diffraction 180 12.11 Scanning Electron Microscope 180 12.12 TEM 180 12.13 EDX 181 12.14 NLO Measurement 181 References 181 Appendix 182 VII Chapter 4.2 [(Ph3P)3Ag2(SeC{O}Ph)2] Results and Discussion A summary of the crystallographic data of 11 and 11a is given in Table 4.1. Compound [(Ph3P)3Ag2(SeC{O}Ph)2] (11) was synthesized by reacting (Ph3P)2Ag(NO3)110 with equal molar of sodium monoselenocarboxylate in MeCN and recrystallized from acetone and hexane solvents. Single crystal of 11 was obtained by dissolving the compound in acetone and layered it with petroleum ether. Compound 11 is less stable in the solution as compared to the copper selenocarboxylate because we observed a change in the color of the reaction solution if the reaction was conducted at room temperature. In addition, such asymmetric dimer compound was not obtained in the case of silver thiocarboxylates. Varying the ratio between the metal salt and the sodium selenocarboxylate does not lead to the formation of other compounds, e. g., mononuclear silver selenocarboxylate. When reacting Ph3P, Ag(NO3) and Na+PhC{O}Se– in 1:1:1 molar ratio, only paste-like compound was obtained. This paste-like product has good solubility in acetone and very unstable in the solution form. After dissolving most of the paste-like compound with acetone, small amount of pale yellow precipitate was remained. This precipitate was later recrystallized by layering the CH2Cl2 solution with hexane. Single crystals were obtained during the recrystallization process. The single crystal was characterized by X-ray crystallography and it turns out to be the tetranuclear compound, [(Ph3P)Ag(SeC{O}Ph)]4 (11a). Unfortunately, due to time constrain, this tetranuclear silver selenocarboxylate is yet to reproduce quantitatively and characterized. 62 Chapter [(Ph3P)3Ag2(SeC{O}Ph)2] Table 4.1. Table summarized the crystallographic data of 11 and 11a. 11 11a Formula C69.25H57.25Ag2N0.25O2.25P3Se2 C51H42Ag2Cl2O2P2Se2 Molecular wt. 1395.47 1193.35 λ, Å 0.71073 0.71073 crystal system Triclinic Monoclinic Space group Pī Pī a,Å 12.843(1) 12.902(1) b,Å 22.636(1) 13.207(1) c,Å 23.928(1) 14.769(1) α,º 109.384(1) 104.456(1) β,º 96.184(1) 100.560(1) 104.860(1) 100.730(1) V,Å 6198.5(4) 2323.5(2) Z ρ, gcm–3 1.495 1.706 –1 1.928 2.633 R1 = 0.1067, wR2 = 0.1388 R1 = 0.0498, wR2 = cell data γ, º µ, mm final R indices (I>2σ(I)) 0.1031 4.2.1 Structures of [(Ph3P)3Ag2(SeC{O}Ph)2] and [(Ph3P)Ag(SeC{O}Ph)]4 In the solid state, compound 11 forms two crystallographically independent asymmetric dimers as illustrated in Figure 4.1. Selected bond lengths (Å) and angles (°) of 11 is shown in Table 4.2. Each of the dimer has similar connectivity as the corresponding copper selenocarboxylate, where the three- and four-coordinates Ag atoms are bridged by two selenium atoms from two benzenecarboselenoate ligands. The geometry at the Ag(2) and Ag(4) are considered as distorted trigonal planar geometry with one Ph3P ligand, which Ag(1) and Ag(3) have a distorted tetrahedral with two Ph3P ligands. The angles around Ag(2) and Ag(4) sum up to 357.03° and 359.86° respectively thus confirms the planar geometry. The tetrahedral angles around 63 Chapter [(Ph3P)3Ag2(SeC{O}Ph)2] Ag(1) and Ag(3) are varies from 90.41(3) – 124.02(4)° and 96.33(3)° – 121.56(3)° respectively. Figure 4.1. Ball and stick diagram of 11. Hydrogen atoms and solvent molecule were removed for clarity. The Ag(1)–P distances, 2.461(1) and 2.473(1) Å are longer than the Ag(2)– P(3) distance, 2.441(1) Å. Similarly, the Ag(3)–P distances, 2.471(1) and 2.473(1) Å are larger than Ag(4)–P distance 2.435(1) Å The observed differences are due to tetrahedral and trigonal planar geometries around the Ag centers. The same is true for the Ag–Se distances, where Ag–Se distances at the Ag(1) (2.783(1) Å and 2.820(1) Å) and Ag(3) (2.727(1) Å and 2.790(1) Å) metal center are longer than those found at Ag(2) (2.605(1) Å and 2.618(1) Å) and Ag(4) (2.623(1) Å and 2.635(1) Å). The disparity in Ag–Se distances due to tetrahedral and trigonal geometries is also found in [(Ph3P)3Ag2(SePh)2].114 The four membered Ag2Se2 rings is planar and approximately assumes the shape of a parallelogram. Each of the Ag2Se2P3 core has an approximate C2 symmetry with the C2-axis passing through either Ag(1), Ag(2), P(3) or Ag(3), Ag(4), P(6) atoms. Further, the two benzenecarboselenoato ligands adopt an anti stereochemistry 64 Chapter [(Ph3P)3Ag2(SeC{O}Ph)2] in the Ag2Se2 ring. The distances between Ag(1)···Ag(2) and Ag(3)···Ag(4), 3.099(1) Å and 2.961(1) Å respectively are less than the sum of the van der Waals radii, 4.25Å and hence the bonds are considered as present.115 Table 4.2. Selected bond lengths (Å) and angles (°) of 11. Bond distances Bond angles Ag(1)-P(2) Ag(1)-P(1) Ag(2)-P(3) Ag(3)-P(5) Ag(3)-P(4) Ag(4)-P(6) Ag(1)-Se(1) Ag(1)-Se(2) Ag(2)-Se(1) Ag(2)-Se(2) Ag(3)-Se(4) Ag(3)-Se(3) Ag(4)-Se(4) Ag(4)-Se(3) 2.461(1) 2.473(1) 2.441(1) 2.470(1) 2.473(1) 2.435(1) 2.782(1) 2.819(1) 2.605(1) 2.618(1) 2.727(1) 2.790(1) 2.623(1) 2.635(1) P(2)-Ag(1)-P(1) P(2)-Ag(1)-Se(1) P(1)-Ag(1)-Se(1) P(2)-Ag(1)-Se(2) P(1)-Ag(1)-Se(2) Se(1)-Ag(1)-Se(2) P(3)-Ag(2)-Se(1) P(3)-Ag(2)-Se(2) Se(1)-Ag(2)-Se(2) Ag(2)-Se(1)-Ag(1) Ag(2)-Se(2)-Ag(1) P(5)-Ag(3)-P(4) P(5)-Ag(3)-Se(4) P(4)-Ag(3)-Se(4) P(5)-Ag(3)-Se(3) P(4)-Ag(3)-Se(3) Se(4)-Ag(3)-Se(3) P(6)-Ag(4)-Se(4) P(6)-Ag(4)-Se(3) Se(4)-Ag(4)-Se(3) Ag(4)-Se(3)-Ag(3) Ag(4)-Se(4)-Ag(3) 124.02(4) 120.84(3) 96.45(3) 90.41(3) 120.95(3) 104.46(2) 117.36(3) 123.74(3) 115.94(2) 70.15(2) 69.37(2) 120.24(5) 121.56(3) 96.51(3) 96.33(3) 115.33(4) 107.41(2) 118.05(4) 126.31(4) 115.50(2) 66.11(2) 67.20(2) Compound 11a is isomorphous and isostructural to the corresponding thiocarboxylate compounds.25 Each of the Ag atom is connected through the Se atom of the selenobenzoate ligand and forms an eight-membered ring Ag4Se4 in the solid state as shown in Figure 4.2. Selected bond lengths (Å) and angles (°) of 11a is shown in Table 4.3. The tetramer ring has crystallographic inversion center in the middle. The 8-membered Ag4Se4 ring appears to be a rectangle when viewed from the top. The Ag···Se distances across the ring are 4.255 Å, which is larger than the van der Waals distance 3.60 Å.87 In addition, the Ag···Ag distance across the ring is 4.255 Å. Hence no cross ring interactions were found in 11a. The Ag–Se distances in 11a are 2.582(1), 2.608(1), 2.537(1) and 2.627(1) comparable with those found in 11. The 65 Chapter [(Ph3P)3Ag2(SeC{O}Ph)2] Ag–P distances in 11a are 2.420(1) and 2.430(1) Å which is comparable to those observed in the corresponding thiocarboxylates.25 Figure 4.2. A view of compound 11a. Hydrogen atoms, phenyl groups on the Ph3P and solvent molecule were deleted for clarity. Table 4.3. Selected bond lengths (Å) and angles (°) of 11a. Bond distances Bond angles Ag(1)-P(1) Ag(1)-Se(2) Ag(1)-Se(1) Ag(2)-P(2) Ag(2)-Se(1) Ag(2)-Se(2)a a 2.420(1) 2.582(1) 2.608(1) 2.430(1) 2.537(1) 2.627(1) P(1)-Ag(1)-Se(2) P(1)-Ag(1)-Se(1) Se(2)-Ag(1)-Se(1) P(2)-Ag(2)-Se(1) P(2)-Ag(2)-Se(2)a Se(1)-Ag(2)-Se(2)a Ag(2)-Se(1)-Ag(1) Ag(1)-Se(2)-Ag(2)a 121.49(2) 126.31(2) 105.82(1) 129.86(2) 110.75(2) 118.70(1) 111.59(1) 91.91(1) Symmetry transformation used to general equivalent atoms: -x+1,-y+1,-z+1 4.2.2 Thermogravimetry and Pyrolysis Experiments Compound 11 is subjected to thermal decomposed under N2 and or vacuum environment. The TGA curve of 11 is shown in Figure 4.3 and the results are summarized in Table 4.4. The decomposed products were further characterized by XRPD as illustrated in Figure 4.4. The XRPD peaks of the pyrolyzed products can be indexed to orthorhombic Ag2Se (JCPDS No. 24-1041). 66 Chapter [(Ph3P)3Ag2(SeC{O}Ph)2] Figure 4.3. Thermogravimetric curves of 11. Table 4.4. Pyrolysis and TGA results for 11. Compd 11 a Temp Residual wt Residual wt Product of range observed. (calc.) from pyrolysisa decomposition (JCPDS (°C) (%) (%) No.) 170 – 314 18.02 (21.5) 19.9 Ag2Se (24-1041) The compound was heated at 500 °C for hours under 0.5 bar. Figure 4.4. XRPD spectrum of the decomposed products of 11, 12 and 13. 67 Chapter 4.3 [(Ph3P)3Ag2(SeC{O}Ph)2] Summary Asymmetric dimer, [(Ph3P)3Ag2(SeC{O}Ph)2] (11) has been synthesized. This compound has similar structure as the copper selenocarboxylate, [(Ph3P)3Cu2(SeC{O}Ph)2] except, two individual dimers were crystallized in the asymmetric unit of 11. Such asymmetrical dimer was not obtained in the case of silver thiocarboxylate. Hence, it reflected the difference in the chemistry between silver thio- and seleno-carboxylates. During the synthesis, we obtained a minor product which is the tetrameric silver selenocarboxylate, [(Ph3P)Ag(SeC{O}Ph)]4 (11a) as confirmed by single crystal X-ray diffraction. Similar to the rest of the metal selenocarboxylates that we have discussed in chapter 3, compound 11 represent a suitable single-source precursor for Ag2Se as supported by XRPD and TGA. In chapter 1, we highlighted the differences in the chemistry between the thioand seleno-carboxylate which were syntheisized by our group.24 Later in chapter and 3, we have shown, in some aspects, the chemistry of metal selenocarboxylate is mimicking the corresponding thiocarboxylate. Here, in this chapter, we illustrated that the chemistry of silver selenocarboxylate is not completely different from the corresponding silver thiocarboxylates. Therefore, at this point of time, we may conclude that, one shall treat the chemistry of metal thiocarboxylate and metal selenocarboxylate distingtively. 4.4 Experimental All starting materials and used reagents are described in chapter 12. All the reactions were performed under the argon atmosphere using standard Shlenk techniques. The synthesis of Na+PhC{O}Se– is described in chapter 3. 68 Chapter [(Ph3P)3Ag2(SeC{O}Ph)2] [(Ph3P)3Ag2(SeC{O}Ph)2], 11 To the Na+PhC{O}Se– (3.02 mmol) solution in 15 mL of MeCN was cooled to ºC, an ice-cold solution of (Ph3P)2Ag(NO3)110 (2.09 g, 3.02 mmol) in mL CH2Cl2 was added very close to the surface using a syringe, to produce a yellow solution. This solution was stirred for h and the insoluble NaCl was filtered off. The solvent from the filtrate was removed and then the yellow solid was dissolved in 10 mL of acetone, layered with ca. 20 mL of hexane and left at ºC overnight to obtain a yellow microcrystalline product. The crystals were filtered and washed with MeOH and a small amount of Et2O, and dried under nitrogen. Yield: 1.68 g (40 %). Elemental Anal.: Calcd. for Ag2P3Se2C68H55O2 (mol wt 1370.76): C, 59.58; H, 4.04 %. 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[Ag(SC{O}Ph)]········································································ Figure 1. 11 TEM images of PbS a) dendrites and b) NRs······························ Figure 1 .12 a) Low resolution and b) high resolution TEM images of the synthesized AgInS2 NPs······························································· Figure 1. 1 6 7 8 9 10 11 12 13 14 18 19 21 Chapter 2 Figure 2 .1 Figure 2.2 Figure 2.3 ESI-MS spectra of [M(SeC{O}Tol)n(SC{O}Ph)3–n]– , n = 0, 1, 2 and 3; M =... describes the synthesis and characterization of a few group 11 , 12 and 13 metal selenocarboxylate complexes The objective of the study is to explore the chemistry of these compounds and the suitability of these as single- source precursors to metal selenide bulk materials and NPs This thesis comprises two parts In the first part (chapter 1 to 3) our discussion is focused on the syntheses and characterization, ... ˚C······················································· Figure 10 .6 XRPD patterns of CuInSe2 NPs synthesized at various temperature Calculated sizes for CuInSe2 NPs based on their XRPD spectra are 8.0 nm (12 5 °C), 25.5 nm (18 0 °C), 12 . 5 nm (200 °C) and 14 .5 (230 °C)·························································· 15 1 15 2 15 3 15 4 15 5 15 6 XXII List of Tables and Schemes Chapter 1 Table 1. 1 Summary on thermal decomposed product of metal thiocarboxylates... of an amine in solution They claimed Ag2S, RN{H}C{O}Ph and H2S gas were produced during the decomposition process .19 In this chapter, the interesting structural chemistry of metal thio- and selenocarboxylates developed in our laboratory and how some of these compounds have been used as precursors for metal sulfides and selenides will be reviewed 1. 2 Group 11 Metal Thio- and Selenocarboxylates 1. 2 .1. .. 10 ·················· Pyrolysis and TGA results for 4 – 10 ··········································· 42 43 46 48 50 Table summarized the crystallographic data of 11 and 11 a········· Selected bond lengths (Å) and angles (°) of 11 ···························· Selected bond lengths (Å) and angles (°) of 11 a·························· Pyrolysis and TGA results for 11 ·················································... and solvent molecule were deleted for clarity··············· Thermogravimetric curves of 11 ·················································· XRPD spectrum of the decomposed products of 11 , 12 and 13 ·· 64 66 67 67 Chapter 5 Schematic illustration of the density of states, along with the changes in the band gap, in semiconductor clusters····················· Figure 5.2 Idealized density of states for. .. Size Control of Ag2Se Nanocrystals from a Single Precursor [(Ph3P)3Ag2(SeC{O}Ph)2] Chem Commun 2005, 3820 (Hot Article) 3 Ng, M T.; Boothroyd, C B.; Vittal, J J One-pot Synthesis of New Phase AgInSe2 Nanorods J Am Chem Soc 2006, 12 8 , 11 78 4 Vittal, J J and Ng, M T Chemistry of Metal Thio- and Selenocarboxylates: Precursors for Metal Sulfide /Selenide Materials, Thin Films and Nanocrystals Acc Chem Res... d-spacings······························································· 14 2 XXIII Chapter 1 Scheme 1. 1 Scheme 1. 2 Scheme 1. 3 Scheme 1. 4 Scheme 1. 5 Scheme 1. 6 Reactivity of copper thiocarboxylates with triphenylphosphine· Solvent dependent interconversion of deformational and conformational isomers of I-6 (R = Me) and I-7 (R = Ph) ········ Views of the ‘claw-like’ [M(SC{O}Ph)3]– ion and its complex with alkali -metal ions··································································... enlarged portion of the cubeshaped Ag2Se crystal is shown at the right hand lower corner···· 10 1 10 2 10 3 10 3 10 4 10 5 10 6 10 7 10 7 Chapter 7 Figure 7 .1 Figure 7.2 Figure 7.3 Figure 7.4 Figure 7.5 Figure 7.6 (a) Low resolution TEM image of Cu2-xSe NCs (b) Zoom in TEM image of twinned Cu2-xSe NCs (c) HRTEM image of a twinned crystal (d) SAED spectrum of Cu2-xSe NPs·················· TEM images of Cu2-xSe NPs . Spectroscopy 17 9 12 . 8 Photoluminescence Spectroscopy 17 9 12 . 9 X-ray Powder Diffraction 18 0 12 . 10 Single Crystal X-ray Diffraction 18 0 12 . 11 Scanning Electron Microscope 18 0 12 . 12 TEM 18 0 12 . 13 . 17 7 12 . 1. 1 Preparation of Na 2 Se and K 2 Se 17 8 12 . 2 Elemental Analysis 17 8 VII 12 . 3 Infrared Spectroscopy 17 9 12 . 4 NMR Spectroscopy 17 9 12 . 5 ESI-MS 17 9 12 . 6 TGA 17 9 12 . 7. I SYNTHESIS AND CHARACTERIZATION OF GROUP 11 , 12 AND 13 METAL SELENOCARBOXYLATES: POTENTIAL SINGLE MOLECULAR PRECURSORS FOR METAL SELENIDE NANOCRYSTALS NG MENG