Synthesis, characterisation and spectroscopic studies of diazine-N-oxide complexes of iron(II) towards the development of sensors
- Authors: Mpiti, Unako Bongani
- Date: 2019
- Subjects: Diazines , Ligands , Iron
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/94753 , vital:31075
- Description: The characteristic magnetic and spectroscopic features associated with the red monomeric or dimeric, and polymeric pyrazine-N-oxide (PyzNO) iron(II) perchlorate complexes; Fen(μ1,1-pyzNO)2n-2(pyzNO)3n+2(ClO4)2n (n = {1, 2}*, and the novel compound {Fe(μ-pyzNO-κN,κO)n-1(pyzNO-κN)2(pyzNO-κO)2}n(ClO4)2n†, respectively, were investigated. These properties are altered substantially when the complexes are hydrated; for instance, by atmospheric exposure. The resulting species; Fe(pyzNO)5(H2O)3(ClO4)2* and [Fe(pyzNO-κN)4(H2O)2](ClO4)2.2H2O†, which have different hues of a bright yellow colour, were found to exhibit strong paramagnetism, in contrast to their anhydrous precursors, which are ‘EPR silent’. A low spin → high spin crossover (LS→HS, SCO) transition was therefore proposed to occur as the complexes become hydrated by atmospheric moisture. The red→yellow colour change is reversible, and dehydration of the yellow species by heating regenerates the red variant, a feature which lends itself to the potential applicability of the system as a sensor. Further emphasis on this potential derives from the fact that the hydration/dehydration process, and its accompanying physical changes, appears reversible even after many such treatments. It became of interest, then, to determine if these changes were limited to water-exposed samples, or if they occurred under more diverse solvent atmospheres. The reversibility of such exposure on the structure of the novel polynuclear complex was therefore investigated. In general, it was found that there occurred a strong solvent-complex association for the more polar solvents. Red→yellow, LS→HS events were seen when the complex was exposed to the vapours of p-dioxane, acetaldehyde and formaldehyde, and to a lesser extent, to that of methanol. In each case, significant structural changes were seen, as evidenced be comparative XRPD and thermo-analytical studies. Some of these changes have however been ascribed to the effects of partial dissolution upon extended exposure of the complex to the associated media. Exposure to less polar solvent atmospheres, such as those of cyclohexane, toluene, diethyl ether, etc., showed some signs of mild solvent surface adhesion, but were unaccompanied by discernible magnetic and colour changes. Another novel complex was produced during attempts to synthesize the PyzNO complexes from a mixture of a 2,2’-dimethoxypropane (DMP) and ethanol (1:1, v/v), rather than the methanol/DMP mixture which had been alternately used. The formula of the resulting complex is Fe(pyzNO)6(ClO4)2.3EtOH*. This EPR inactive product was orange in colour, and transformed into a bright yellow, strongly paramagnetic species upon atmospheric exposure. Further solvent studies showed that this species interacted significantly with all solvents tested, but generally more strongly with increasing solvent polarity. Orange→yellow colour changes occurred in environments saturated with p-dioxane, acetaldehyde and formaldehyde vapours. The DMSO-exposed sample transformed to dark red, due to suspected PyzNO substitution by the solvent. The red→yellow and orange→yellow colour changes were ascribed to the formal substitution of O-coordinated PyzNO (μ-PyzNO in the polymeric complex) by the incoming solvent. The resulting structural and geometric changes stimulated a redistribution of d electrons among the new constituent molecular orbitals of altered energy and symmetry. Therefore, although the colour changes were not conventionally solvatochromic - in that the original structure was lost on exposure – data suggested that it was the coordination of species of higher donor strength that produced the observed bathochromic shifts. A novel 4,4’-bipyridine-N-oxide Fe(II) perchlorate complex, Fe2(bipyNO)5(ClO4)4.6MeOH†, was also produced, primarily for physicochemical comparison with the PyzNO complexes. No colour or magnetic changes were seen on atmospheric exposure. The original complex was observed to be inherently paramagnetic, and no SCO events occurred upon solvent exposure. Despite this, thermal analyses showed that the complex did exhibit the strong uptake of polar solvents in general, but particularly with acetaldehyde. Significant structural changes upon exposure were limited to surface phenomena, with the exception of the acetaldehyde-exposed sample.
- Full Text:
- Date Issued: 2019
- Authors: Mpiti, Unako Bongani
- Date: 2019
- Subjects: Diazines , Ligands , Iron
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/94753 , vital:31075
- Description: The characteristic magnetic and spectroscopic features associated with the red monomeric or dimeric, and polymeric pyrazine-N-oxide (PyzNO) iron(II) perchlorate complexes; Fen(μ1,1-pyzNO)2n-2(pyzNO)3n+2(ClO4)2n (n = {1, 2}*, and the novel compound {Fe(μ-pyzNO-κN,κO)n-1(pyzNO-κN)2(pyzNO-κO)2}n(ClO4)2n†, respectively, were investigated. These properties are altered substantially when the complexes are hydrated; for instance, by atmospheric exposure. The resulting species; Fe(pyzNO)5(H2O)3(ClO4)2* and [Fe(pyzNO-κN)4(H2O)2](ClO4)2.2H2O†, which have different hues of a bright yellow colour, were found to exhibit strong paramagnetism, in contrast to their anhydrous precursors, which are ‘EPR silent’. A low spin → high spin crossover (LS→HS, SCO) transition was therefore proposed to occur as the complexes become hydrated by atmospheric moisture. The red→yellow colour change is reversible, and dehydration of the yellow species by heating regenerates the red variant, a feature which lends itself to the potential applicability of the system as a sensor. Further emphasis on this potential derives from the fact that the hydration/dehydration process, and its accompanying physical changes, appears reversible even after many such treatments. It became of interest, then, to determine if these changes were limited to water-exposed samples, or if they occurred under more diverse solvent atmospheres. The reversibility of such exposure on the structure of the novel polynuclear complex was therefore investigated. In general, it was found that there occurred a strong solvent-complex association for the more polar solvents. Red→yellow, LS→HS events were seen when the complex was exposed to the vapours of p-dioxane, acetaldehyde and formaldehyde, and to a lesser extent, to that of methanol. In each case, significant structural changes were seen, as evidenced be comparative XRPD and thermo-analytical studies. Some of these changes have however been ascribed to the effects of partial dissolution upon extended exposure of the complex to the associated media. Exposure to less polar solvent atmospheres, such as those of cyclohexane, toluene, diethyl ether, etc., showed some signs of mild solvent surface adhesion, but were unaccompanied by discernible magnetic and colour changes. Another novel complex was produced during attempts to synthesize the PyzNO complexes from a mixture of a 2,2’-dimethoxypropane (DMP) and ethanol (1:1, v/v), rather than the methanol/DMP mixture which had been alternately used. The formula of the resulting complex is Fe(pyzNO)6(ClO4)2.3EtOH*. This EPR inactive product was orange in colour, and transformed into a bright yellow, strongly paramagnetic species upon atmospheric exposure. Further solvent studies showed that this species interacted significantly with all solvents tested, but generally more strongly with increasing solvent polarity. Orange→yellow colour changes occurred in environments saturated with p-dioxane, acetaldehyde and formaldehyde vapours. The DMSO-exposed sample transformed to dark red, due to suspected PyzNO substitution by the solvent. The red→yellow and orange→yellow colour changes were ascribed to the formal substitution of O-coordinated PyzNO (μ-PyzNO in the polymeric complex) by the incoming solvent. The resulting structural and geometric changes stimulated a redistribution of d electrons among the new constituent molecular orbitals of altered energy and symmetry. Therefore, although the colour changes were not conventionally solvatochromic - in that the original structure was lost on exposure – data suggested that it was the coordination of species of higher donor strength that produced the observed bathochromic shifts. A novel 4,4’-bipyridine-N-oxide Fe(II) perchlorate complex, Fe2(bipyNO)5(ClO4)4.6MeOH†, was also produced, primarily for physicochemical comparison with the PyzNO complexes. No colour or magnetic changes were seen on atmospheric exposure. The original complex was observed to be inherently paramagnetic, and no SCO events occurred upon solvent exposure. Despite this, thermal analyses showed that the complex did exhibit the strong uptake of polar solvents in general, but particularly with acetaldehyde. Significant structural changes upon exposure were limited to surface phenomena, with the exception of the acetaldehyde-exposed sample.
- Full Text:
- Date Issued: 2019
Carbonate petrography and geochemistry of BIF of the Transvaal supergroup : evaluating the potential of iron carbonates as proxies for palaeoproterozoic ocean chemistry
- Authors: Rafuza, Sipesihle
- Date: 2015
- Subjects: Carbonate rocks -- South Africa -- Transvaal Supergroup , Petrology -- South Africa -- Transvaal Supergroup , Geochemistry -- South Africa -- Transvaal Supergroup , Petrology -- South Africa -- Kuruman , Petrology -- South Africa -- Griekwastad , Geology, Stratigraphic -- Proterozoic , Chemical oceanography , Iron
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5089 , http://hdl.handle.net/10962/d1018611
- Description: The subject of BIF genesis, particularly their environmental conditions and ocean chemistry at the time of deposition and their evolution through time, has been a subject of much contentiousness, generating a wealth of proposed genetic models and constant refinements thereof over the years. The prevailing paradigm within the various schools of thought, is the widespread and generally agreed upon depositional and diagenetic model(s) which advocate for BIF deposition under anoxic marine conditions. According to the prevailing models, the primary depositional environment would have involved a seawater column whereby soluble Fe²⁺ expelled by hydrothermal activity mixed with free O₂ from the shallow photic zone produced by eukaryotes, forming a high valence iron oxy-hydroxide precursor such as FeOOH or Fe(OH)₃. An alternative biological mechanism producing similar ferric precursors would have been in the form of photo-ferrotrophy, whereby oxidation of ferrous iron to the ferric form took place in the absence of biological O₂ production. Irrespective of the exact mode of primary iron precipitation (which remains contentious to date), the precipitated ferric oxy-hydroxide precursor would have reacted with co-precipitated organic matter, thus acting as a suitable electron acceptor for organic carbon remineralisation through Dissimilatory Iron Reduction (DIR), as also observed in many modern anoxic diagenetic environments. DIR-dominated diagenetic models imply a predominantly diagenetic influence in BIF mineralogy and genesis, and use as key evidence the low δ¹³C values relative to the seawater bicarbonate value of ~0 ‰, which is also thought to have been the dissolved bicarbonate isotope composition in the early Precambrian oceans. The carbon for diagenetic carbonate formation would thus have been sourced through a combination of two end-member sources: pore-fluid bicarbonate at ~0 ‰ and particulate organic carbon at circa -28 ‰, resulting in the intermediate δ¹³C values observed in BIFs today. This study targets 65 drillcore samples of the upper Kuruman and Griquatown BIF from the lower Transvaal Supergroup in the Hotazel area, Northern Cape, South Africa, and sets out to explore key aspects in BIF carbonate petrography and geochemistry that are pertinent to current debates surrounding their interpretation with regard to primary versus diagenetic processes. The focus here rests on applications of carbonate (mainly siderite and ankerite) petrography, mineral chemistry, bulk and mineral-specific carbon isotopes and speciation analyses, with a view to obtaining valuable new insights into BIF carbonates as potential records of ocean chemistry for their bulk carbonate-carbon isotope signature. Evaluation of the present results is done in light of pre-existing, widely accepted diagenetic models against a proposed water-column model for the origin of the carbonate species in BIF. The latter utilises a combination of geochemical attributes of the studied carbonates, including the conspicuous Mn enrichment and stratigraphic variability in Mn/Fe ratio of the Griquatown BIF recorded solely in the carbonate fraction of the rocks. Additionally, the carbon isotope signatures of the Griquatown BIF samples are brought into the discussion and provide insights into the potential causes and mechanisms that may have controlled these signatures in a diagenetic versus primary sedimentary environment. Ultimately, implications of the combined observations, findings and arguments presented in this thesis are presented and discussed with particular respect to the redox evolution and carbon cycle of the ocean system prior to the Great Oxidation Event (GOE). A crucial conclusion reached is that, by contrast to previously-proposed models, diagenesis cannot singularly be the major contributing factor in BIF genesis at least with respect to the carbonate fraction in BIF, as it does not readily explain the carbon isotope and mineral-chemical signatures of carbonates in the Griquatown and uppermost Kuruman BIFs. It is proposed instead that these signatures may well record water-column processes of carbon, manganese and iron cycling, and that carbonate formation in the water column and its subsequent transfer to the precursor BIF sediment constitutes a faithful record of such processes. Corollary to that interpretation is the suggestion that the evidently increasing Mn abundance in the carbonate fraction of the Griquatown BIF up-section would point to a chemically evolving depositional basin with time, from being mainly ferruginous as expressed by Mn-poor BIFs in the lower stratigraphic sections (i.e. Kuruman BF) to more manganiferous as recorded in the upper Griquatown BIF, culminating in the deposition of the abnormally enriched in Mn Hotazel BIF at the stratigraphic top of the Transvaal Supergroup. The Paleoproterozoic ocean must therefore have been characterised by long-term active cycling of organic carbon in the water column in the form of an ancient biological pump, albeit with Fe(III) and subsequently Mn(III,IV) oxy-hydroxides being the key electron acceptors within the water column. The highly reproducible stratigraphic isotope profiles for bulk δ¹³C from similar sections further afield over distances up to 20 km, further corroborate unabatedly that bulk carbonate carbon isotope signatures record water column carbon cycling processes rather than widely-proposed anaerobic diagenetic processes.
- Full Text:
- Date Issued: 2015
- Authors: Rafuza, Sipesihle
- Date: 2015
- Subjects: Carbonate rocks -- South Africa -- Transvaal Supergroup , Petrology -- South Africa -- Transvaal Supergroup , Geochemistry -- South Africa -- Transvaal Supergroup , Petrology -- South Africa -- Kuruman , Petrology -- South Africa -- Griekwastad , Geology, Stratigraphic -- Proterozoic , Chemical oceanography , Iron
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5089 , http://hdl.handle.net/10962/d1018611
- Description: The subject of BIF genesis, particularly their environmental conditions and ocean chemistry at the time of deposition and their evolution through time, has been a subject of much contentiousness, generating a wealth of proposed genetic models and constant refinements thereof over the years. The prevailing paradigm within the various schools of thought, is the widespread and generally agreed upon depositional and diagenetic model(s) which advocate for BIF deposition under anoxic marine conditions. According to the prevailing models, the primary depositional environment would have involved a seawater column whereby soluble Fe²⁺ expelled by hydrothermal activity mixed with free O₂ from the shallow photic zone produced by eukaryotes, forming a high valence iron oxy-hydroxide precursor such as FeOOH or Fe(OH)₃. An alternative biological mechanism producing similar ferric precursors would have been in the form of photo-ferrotrophy, whereby oxidation of ferrous iron to the ferric form took place in the absence of biological O₂ production. Irrespective of the exact mode of primary iron precipitation (which remains contentious to date), the precipitated ferric oxy-hydroxide precursor would have reacted with co-precipitated organic matter, thus acting as a suitable electron acceptor for organic carbon remineralisation through Dissimilatory Iron Reduction (DIR), as also observed in many modern anoxic diagenetic environments. DIR-dominated diagenetic models imply a predominantly diagenetic influence in BIF mineralogy and genesis, and use as key evidence the low δ¹³C values relative to the seawater bicarbonate value of ~0 ‰, which is also thought to have been the dissolved bicarbonate isotope composition in the early Precambrian oceans. The carbon for diagenetic carbonate formation would thus have been sourced through a combination of two end-member sources: pore-fluid bicarbonate at ~0 ‰ and particulate organic carbon at circa -28 ‰, resulting in the intermediate δ¹³C values observed in BIFs today. This study targets 65 drillcore samples of the upper Kuruman and Griquatown BIF from the lower Transvaal Supergroup in the Hotazel area, Northern Cape, South Africa, and sets out to explore key aspects in BIF carbonate petrography and geochemistry that are pertinent to current debates surrounding their interpretation with regard to primary versus diagenetic processes. The focus here rests on applications of carbonate (mainly siderite and ankerite) petrography, mineral chemistry, bulk and mineral-specific carbon isotopes and speciation analyses, with a view to obtaining valuable new insights into BIF carbonates as potential records of ocean chemistry for their bulk carbonate-carbon isotope signature. Evaluation of the present results is done in light of pre-existing, widely accepted diagenetic models against a proposed water-column model for the origin of the carbonate species in BIF. The latter utilises a combination of geochemical attributes of the studied carbonates, including the conspicuous Mn enrichment and stratigraphic variability in Mn/Fe ratio of the Griquatown BIF recorded solely in the carbonate fraction of the rocks. Additionally, the carbon isotope signatures of the Griquatown BIF samples are brought into the discussion and provide insights into the potential causes and mechanisms that may have controlled these signatures in a diagenetic versus primary sedimentary environment. Ultimately, implications of the combined observations, findings and arguments presented in this thesis are presented and discussed with particular respect to the redox evolution and carbon cycle of the ocean system prior to the Great Oxidation Event (GOE). A crucial conclusion reached is that, by contrast to previously-proposed models, diagenesis cannot singularly be the major contributing factor in BIF genesis at least with respect to the carbonate fraction in BIF, as it does not readily explain the carbon isotope and mineral-chemical signatures of carbonates in the Griquatown and uppermost Kuruman BIFs. It is proposed instead that these signatures may well record water-column processes of carbon, manganese and iron cycling, and that carbonate formation in the water column and its subsequent transfer to the precursor BIF sediment constitutes a faithful record of such processes. Corollary to that interpretation is the suggestion that the evidently increasing Mn abundance in the carbonate fraction of the Griquatown BIF up-section would point to a chemically evolving depositional basin with time, from being mainly ferruginous as expressed by Mn-poor BIFs in the lower stratigraphic sections (i.e. Kuruman BF) to more manganiferous as recorded in the upper Griquatown BIF, culminating in the deposition of the abnormally enriched in Mn Hotazel BIF at the stratigraphic top of the Transvaal Supergroup. The Paleoproterozoic ocean must therefore have been characterised by long-term active cycling of organic carbon in the water column in the form of an ancient biological pump, albeit with Fe(III) and subsequently Mn(III,IV) oxy-hydroxides being the key electron acceptors within the water column. The highly reproducible stratigraphic isotope profiles for bulk δ¹³C from similar sections further afield over distances up to 20 km, further corroborate unabatedly that bulk carbonate carbon isotope signatures record water column carbon cycling processes rather than widely-proposed anaerobic diagenetic processes.
- Full Text:
- Date Issued: 2015
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