A Comparative study of two copper(II) based metal-organic frameworks : Cu2¼(OH)½B4C•8H2O and Cu2Na(OH)B4C•7H2O
- Authors: Coombes, Matthew
- Date: 2013
- Subjects: Copper , Organometallic compounds , Supramolecular organometallic chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4533 , http://hdl.handle.net/10962/d1016245
- Description: This study focussed on two copper(II)-containing metal-organic frameworks (MOFs): Cu2Na(OH)B4C•7H2O and Cu2¼(OH)½B4C•8H2O (B4C = 1,2,4,5- benzenetetracarboxylate). They are both covalent, three-dimensional metalorganic framework polymers containing voids filled with water molecules. Both were characterised by elemental analysis, infrared spectroscopy, X-ray powder diffractometry (both in situ and regular), thermogravimetric analysis, differential scanning calorimetry and X-ray photoelectron spectroscopy. These two MOFs are essentially identical, with the only difference being the substitution of sodium by copper at every 4th site (disordered throughout the crystal). The guest inclusion properties of both MOFs were studied and compared. Although both structures collapse on dehydration, it was observed that Cu2Na(OH)B4C•7H2O is able to take up signifcant amounts of water, methanol and ethanol. All these processes are fully reversible. Car-Parrinello molecular dynamics studies suggest that it is a strong interaction between the oxygen atoms on these molecules with the sodium cation of the MOF that is responsible for this signifcant uptake. In contrast, Cu2¼ (OH)½ B4C•8H2O, the MOF without a sodium cation, did not demonstrate any methanol or ethanol uptake, but was able to take up some water. The uptake of water, however, is not a fully reversible process. The absence of sodium likely results in insuffcient energy to draw methanol and ethanol into the framework, while a subtle rotation of a carboxylate group on dehydration decreases the ability of the framework to form hydrogen bonds, thus reducing the ability to take up water. A series of hydrothermal syntheses were performed in order to develop a method of synthesis superior to the current gel-based synthesis that requires several months and has poor yields. The hydrothermal products were characterized by elemental analysis, infrared spectroscopy, X-ray powder diffractometry, thermogravimetric analysis and differential scanning calorimetry. It was shown that the MOF Cu2Na(OH)B4C•7H2O may be synthesised in almost 100% yield by using a temperature of 120°C over a period of 72 hours. It was not possible to synthesise Cu2¼ (OH)½ B4C•8H2O in a 100% yield - it was only obtained as a minor product.
- Full Text:
- Date Issued: 2013
- Authors: Coombes, Matthew
- Date: 2013
- Subjects: Copper , Organometallic compounds , Supramolecular organometallic chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4533 , http://hdl.handle.net/10962/d1016245
- Description: This study focussed on two copper(II)-containing metal-organic frameworks (MOFs): Cu2Na(OH)B4C•7H2O and Cu2¼(OH)½B4C•8H2O (B4C = 1,2,4,5- benzenetetracarboxylate). They are both covalent, three-dimensional metalorganic framework polymers containing voids filled with water molecules. Both were characterised by elemental analysis, infrared spectroscopy, X-ray powder diffractometry (both in situ and regular), thermogravimetric analysis, differential scanning calorimetry and X-ray photoelectron spectroscopy. These two MOFs are essentially identical, with the only difference being the substitution of sodium by copper at every 4th site (disordered throughout the crystal). The guest inclusion properties of both MOFs were studied and compared. Although both structures collapse on dehydration, it was observed that Cu2Na(OH)B4C•7H2O is able to take up signifcant amounts of water, methanol and ethanol. All these processes are fully reversible. Car-Parrinello molecular dynamics studies suggest that it is a strong interaction between the oxygen atoms on these molecules with the sodium cation of the MOF that is responsible for this signifcant uptake. In contrast, Cu2¼ (OH)½ B4C•8H2O, the MOF without a sodium cation, did not demonstrate any methanol or ethanol uptake, but was able to take up some water. The uptake of water, however, is not a fully reversible process. The absence of sodium likely results in insuffcient energy to draw methanol and ethanol into the framework, while a subtle rotation of a carboxylate group on dehydration decreases the ability of the framework to form hydrogen bonds, thus reducing the ability to take up water. A series of hydrothermal syntheses were performed in order to develop a method of synthesis superior to the current gel-based synthesis that requires several months and has poor yields. The hydrothermal products were characterized by elemental analysis, infrared spectroscopy, X-ray powder diffractometry, thermogravimetric analysis and differential scanning calorimetry. It was shown that the MOF Cu2Na(OH)B4C•7H2O may be synthesised in almost 100% yield by using a temperature of 120°C over a period of 72 hours. It was not possible to synthesise Cu2¼ (OH)½ B4C•8H2O in a 100% yield - it was only obtained as a minor product.
- Full Text:
- Date Issued: 2013
An experimental and theoretical investigation of unstable Fischer chromium carbene complexes
- Authors: Makanjee, Che Azad
- Date: 2013 , 2013-03-27
- Subjects: Chromium , Organolithium compounds , Carbenes (Methylene compounds) , Organometallic chemistry , Organometallic compounds , Organochromium compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4284 , http://hdl.handle.net/10962/d1002953 , Chromium , Organolithium compounds , Carbenes (Methylene compounds) , Organometallic chemistry , Organometallic compounds , Organochromium compounds
- Description: This organometallic study involves the use organostannanes and organolithiums as precursors to chromium Fischer carbene complexes. Fischer carbenes are typically electrophilic and are stabilized by a single π-donor substituent, and contain low oxidation state metals (often but not always from Group 6). They are highly reactive and can give access to a range of biologically active compounds through cyclopropanations, insertions, coupling and photochemical reactions. Synthesis and characterization of three MOM-protected α-alkoxy organostannanes was successfully carried out via a nucleophilic addition of tributylstannyllithium to suitable aldehydes, and immediate protection of the alcohol with MOM. Two N-BOC protected α-amino organostannanes were successfully synthesized and characterized via α-lithiation and tin-lithium exchange in the presence of TMEDA. Tin-lithium transmetallation of the organostannanes allowed access to the organolithiums required for the synthesis of novel Fischer carbenes. Addition of chromium hexacarbonyl to the organolithiums formed the acylpentacarbonyl chromate salt which was alkylated with Meerwein salt, resulting in the Fischer carbene and a by-product, tetrabutyltin, which proved difficult to remove. Several Fischer carbenes were synthesized and characterized, some simple and known and some novel. In silico work explored the reaction coordinate of the [2+2] cycloaddition towards the formation of β-lactams, and the photoactivation cycle that precedes this process. Computational work also showed the effect of the ligand on the stability and reactivity of the carbene. It was found that in some cases the oxygen on the ligand could negatively influence the stability of the carbene (when compared to a simple methyl carbene). A link between bond orders and back donation in Fischer carbenes was explored in an attempt to theoretically predict the stability of a range of carbenes. , Microsoft� Office Word 2007
- Full Text:
- Date Issued: 2013
- Authors: Makanjee, Che Azad
- Date: 2013 , 2013-03-27
- Subjects: Chromium , Organolithium compounds , Carbenes (Methylene compounds) , Organometallic chemistry , Organometallic compounds , Organochromium compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4284 , http://hdl.handle.net/10962/d1002953 , Chromium , Organolithium compounds , Carbenes (Methylene compounds) , Organometallic chemistry , Organometallic compounds , Organochromium compounds
- Description: This organometallic study involves the use organostannanes and organolithiums as precursors to chromium Fischer carbene complexes. Fischer carbenes are typically electrophilic and are stabilized by a single π-donor substituent, and contain low oxidation state metals (often but not always from Group 6). They are highly reactive and can give access to a range of biologically active compounds through cyclopropanations, insertions, coupling and photochemical reactions. Synthesis and characterization of three MOM-protected α-alkoxy organostannanes was successfully carried out via a nucleophilic addition of tributylstannyllithium to suitable aldehydes, and immediate protection of the alcohol with MOM. Two N-BOC protected α-amino organostannanes were successfully synthesized and characterized via α-lithiation and tin-lithium exchange in the presence of TMEDA. Tin-lithium transmetallation of the organostannanes allowed access to the organolithiums required for the synthesis of novel Fischer carbenes. Addition of chromium hexacarbonyl to the organolithiums formed the acylpentacarbonyl chromate salt which was alkylated with Meerwein salt, resulting in the Fischer carbene and a by-product, tetrabutyltin, which proved difficult to remove. Several Fischer carbenes were synthesized and characterized, some simple and known and some novel. In silico work explored the reaction coordinate of the [2+2] cycloaddition towards the formation of β-lactams, and the photoactivation cycle that precedes this process. Computational work also showed the effect of the ligand on the stability and reactivity of the carbene. It was found that in some cases the oxygen on the ligand could negatively influence the stability of the carbene (when compared to a simple methyl carbene). A link between bond orders and back donation in Fischer carbenes was explored in an attempt to theoretically predict the stability of a range of carbenes. , Microsoft� Office Word 2007
- Full Text:
- Date Issued: 2013
Atmospheric pressure metal-organic vapour phase epitaxial growth of InAs/GaSb strained layer superlattices
- Authors: Miya, Senzo Simo
- Date: 2013
- Subjects: Gallium arsenide semiconductors , Organometallic compounds , Compound semiconductors , Metal organic chemical vapor deposition , Superlattices as materials , Epitaxy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10557 , http://hdl.handle.net/10948/d1020866
- Description: The importance of infrared (IR) technology (for detection in the 3-5 μm and 8-14 μm atmospheric windows) has spread from military applications to civilian applications since World War II. The commercial IR detector market in these wavelength ranges is dominated by mercury cadmium telluride (MCT) alloys. The use of these alloys has, however, been faced with technological difficulties. One of the materials that have been tipped to be suitable to replace MCT is InAs/InxGa1-xSb strained layer superlattices (SLS’s). Atmospheric pressure metal-organic vapour phase epitaxy (MOVPE) has been used to grow InAs/GaSb strained layer superlattices (SLS’s) at 510 °C in this study. This is a starting point towards the development of MOVPE InAs/InxGa1-xSb SLS’s using the same system. Before the SLS’s could be attempted, the growth parameters for GaSb were optimised. Growth parameters for InAs were taken from reports on previous studies conducted using the same reactor. Initially, trimethylgallium, a source that has been used extensively in the same growth system for the growth of GaSb and InxGa1-xSb was intended to be used for gallium species. The high growth rates yielded by this source were too large for the growth of SLS structures, however. Thus, triethylgallium (rarely used for atmospheric pressure MOVPE) was utilized. GaSb layers (between 1 and 2 μm thick) were grown at two different temperatures (550 °C and 510 °C) with a varying V/III ratio. A V/III ratio of 1.5 was found to be optimal at 550 °C. However, the low incorporation efficiency of indium into GaSb at this temperature was inadequate to obtain InxGa1-xSb with an indium mole fraction (x) of around 0.3, which had previously been reported to be optimal for the performance of InAs/InxGa1-xSb SLS’s, due to the maximum splitting of the valence mini bands for this composition. The growth temperature was thus lowered to 510 °C. This resulted in an increase in the optimum V/III ratio to 1.75 for GaSb and yielded much higher incorporation efficiencies of indium in InxGa1-xSb. However, this lower growth temperature also produced poorer surface morphologies for both the binary and ternary layers, due to the reduced surface diffusion of the adsorbed species. An interface control study during the growth of InAs/GaSb SLS’s was subsequently conducted, by investigating the influence of different gas switching sequences on the interface type and quality. It was noted that the growth of SLS’s without any growth interruptions at the interfaces leads to tensile strained SLS’s (GaAs-like interfaces) with a rather large lattice mismatch. A 5 second flow of TMSb over the InAs surface and a flow of H2 over GaSb surface yielded compressively strained SLS’s. Flowing TMIn for 1 second and following by a flow of TMSb for 4 seconds over the GaSb surface, while flowing H2 for 5 seconds over the InAs surface, resulted in SLS’s with GaAs-like interfacial layers and a reduced lattice mismatch. Temperature gradients across the surface of the susceptor led to SLS’s with different structural quality. High resolution x-ray diffraction (HRXRD) was used to determine the thicknesses as well as the type of interfacial layers. The physical parameters of the SLS’s obtained from simulating the HRXRD spectra were comparable to the parameters obtained from cross sectional transmission electron microscopy (XTEM) images. The thicknesses of the layers and the interface type played a major role in determining the cut-off wavelength of the SLS’s.
- Full Text:
- Date Issued: 2013
- Authors: Miya, Senzo Simo
- Date: 2013
- Subjects: Gallium arsenide semiconductors , Organometallic compounds , Compound semiconductors , Metal organic chemical vapor deposition , Superlattices as materials , Epitaxy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10557 , http://hdl.handle.net/10948/d1020866
- Description: The importance of infrared (IR) technology (for detection in the 3-5 μm and 8-14 μm atmospheric windows) has spread from military applications to civilian applications since World War II. The commercial IR detector market in these wavelength ranges is dominated by mercury cadmium telluride (MCT) alloys. The use of these alloys has, however, been faced with technological difficulties. One of the materials that have been tipped to be suitable to replace MCT is InAs/InxGa1-xSb strained layer superlattices (SLS’s). Atmospheric pressure metal-organic vapour phase epitaxy (MOVPE) has been used to grow InAs/GaSb strained layer superlattices (SLS’s) at 510 °C in this study. This is a starting point towards the development of MOVPE InAs/InxGa1-xSb SLS’s using the same system. Before the SLS’s could be attempted, the growth parameters for GaSb were optimised. Growth parameters for InAs were taken from reports on previous studies conducted using the same reactor. Initially, trimethylgallium, a source that has been used extensively in the same growth system for the growth of GaSb and InxGa1-xSb was intended to be used for gallium species. The high growth rates yielded by this source were too large for the growth of SLS structures, however. Thus, triethylgallium (rarely used for atmospheric pressure MOVPE) was utilized. GaSb layers (between 1 and 2 μm thick) were grown at two different temperatures (550 °C and 510 °C) with a varying V/III ratio. A V/III ratio of 1.5 was found to be optimal at 550 °C. However, the low incorporation efficiency of indium into GaSb at this temperature was inadequate to obtain InxGa1-xSb with an indium mole fraction (x) of around 0.3, which had previously been reported to be optimal for the performance of InAs/InxGa1-xSb SLS’s, due to the maximum splitting of the valence mini bands for this composition. The growth temperature was thus lowered to 510 °C. This resulted in an increase in the optimum V/III ratio to 1.75 for GaSb and yielded much higher incorporation efficiencies of indium in InxGa1-xSb. However, this lower growth temperature also produced poorer surface morphologies for both the binary and ternary layers, due to the reduced surface diffusion of the adsorbed species. An interface control study during the growth of InAs/GaSb SLS’s was subsequently conducted, by investigating the influence of different gas switching sequences on the interface type and quality. It was noted that the growth of SLS’s without any growth interruptions at the interfaces leads to tensile strained SLS’s (GaAs-like interfaces) with a rather large lattice mismatch. A 5 second flow of TMSb over the InAs surface and a flow of H2 over GaSb surface yielded compressively strained SLS’s. Flowing TMIn for 1 second and following by a flow of TMSb for 4 seconds over the GaSb surface, while flowing H2 for 5 seconds over the InAs surface, resulted in SLS’s with GaAs-like interfacial layers and a reduced lattice mismatch. Temperature gradients across the surface of the susceptor led to SLS’s with different structural quality. High resolution x-ray diffraction (HRXRD) was used to determine the thicknesses as well as the type of interfacial layers. The physical parameters of the SLS’s obtained from simulating the HRXRD spectra were comparable to the parameters obtained from cross sectional transmission electron microscopy (XTEM) images. The thicknesses of the layers and the interface type played a major role in determining the cut-off wavelength of the SLS’s.
- Full Text:
- Date Issued: 2013
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