This thesis investigates the synthesis and activation of highly monodisperse Au25(SR)18 - clusters and bimetallic clusters (AuAg and AuPd) protected with various stabilizers for reduction and hydrogenation catalytic reactions. The first chapter is the introduction chapter, which summarizes the literature involving monolayer protected Au clusters, atomically precise Au clusters, bimetallic clusters, X-ray absorption spectroscopy, research objectives, and organization and scope. The second chapter describes the synthesis of Au25(SR)18 - clusters protected with various thiolate stabilizers for nitrophenol reduction catalysis using NaBH4 as a reducing agent. This chapter also describes the stability of these clusters under reaction conditions using UV-Vis spectroscopy and MALDI mass spectrometry. The third chapter details the synthesis of carboxylic acid-protected Au25 clusters using a NaBH4 purification strategy. Here, the knowledge obtained in the second chapter regarding the exceptional stability of Au25(SR)18 - clusters in the presence of NaBH4 was used to isolate carboxylic acid protected Au25 clusters from a polydisperse reaction mixture. The fourth chapter describes the synthesis and activation of mesoporous carbon supported Au25(SR)18 - clusters for nitrophenol reduction catalysis. Here, thermal removal of thiolate stabilizers led to the enhancement in the catalytic activity at low calcination temperatures; however, at higher calcination temperatures activity dropped as particle sintering was observed. Activation of these clusters on mesoporous carbon support was followed by TEM and X-ray absorption spectroscopy. The fifth chapter describes the thermal and chemical removal of thiolate stabilizers from supported Au25(SC8H9)18 - clusters. Here, the removal of thiolate stabilizers and subsequent growth of Au25 clusters was followed by TEM and EXAFS spectroscopy. The sixth and seventh chapters describe the synthesis of AuPd and AuAg bimetallic clusters using Au25(SR)18 - clusters as precursors and their characterization using UV-Vis spectroscopy, transmission electron microscopy, and X-ray absorption spectroscopy. Here, AuPd bimetallic clusters were thermally and chemically treated, which resulted in the formation of AuPd bimetallic nanoparticles with segregated Pd atoms on the surface. AuPd bimetallic nanoparticles were used for the selective hydrogenation catalysis of allyl alcohol. The last chapter of this thesis includes final conclusions and possible avenues for future work.

Despite previous extensive study of the widely-employed ruthenium-catalysed olefin metathesis reaction, the finer mechanistic details have not been elucidated. An area that is noticeably lacking is spectroscopic exploration of the relevant complexes. In this work, organometallic ruthenium complexes of importance to olefin metathesis have been investigated using Ru K-edge X-ray absorption spectroscopy. The lowest energy feature in the Ru K-edge spectrum has been unambiguously assigned as due to Ru 4d←1s transitions. These electric-dipole-forbidden transitions are extremely sensitive to geometry. For centrosymmetric complexes, the pre-edge feature has very low intensity because it is limited by the weak electric quadrupole mechanism. By contrast, non-centrosymmetric complexes exhibit a substantial increase in pre-edge intensity because Ru 5p-4d mixing introduces electric-dipole-allowed character to the Ru 4d←1s transitions. The energy of the edge feature in the Ru K-edge spectrum corresponds to ionisation of 1s electrons and is a good indicator of the charge on the metal centre. Unexpectedly, we found that the first-generation (L = PCy₃) Grubbs precatalyst (1) has a higher 1s ionisation energy than the second-generation (L = H₂IMes) complex (2). This effect provides a compelling rationale for the unexplained differences in phosphine dissociation kinetics for complexes 1 and 2: the phosphine dissociation rate of 2 is slower than 1 because the metal centre is more electron-deficient in 2. Density functional theory calculations confirm the charge differences and offer some insight into the nature of bonding in these complexes, particularly with regard to the N-heterocyclic carbene and trialkylphosphine ligands. On the basis of these results, we propose that, for this system, the NHC ligand is a weaker σ-charge donor than the phosphine ligand, and that the NHC accepts significant π-electron density from the metal; both interactions function to reduce the electron density on the ruthenium centre. An ultimate goal is to investigate reactive species in the olefin metathesis mechanism; accordingly, we have made considerable progress toward collecting XAS data for a metallacyclobutane species, and we are pursuing methods to trap the four-coordinate intermediate in the metathesis cycle.

X-ray absorption spectroscopy (XAS) is a powerful probe of electronic and spatial structure that has been at the heart of many advances in physics, biology, chemistry, engineering and the earth sciences. Unfortunately, the existing experimental techniques are subject to fundamental limitations that complicate the interpretation of x-ray absorption spectra in many important cases. These limitations have motivated an effort to develop an alternative measure of the absorption cross-section that is not subject to the same set of limitations. In this thesis, a technique known as inverse partial fluorescence yield (IPFY) is described which addresses this problem. IPFY differs from existing approaches in a significant way — by using an energy-discriminating photon detector, one gains access to fluorescence information from both resonant and non-resonant x-ray emission processes. We will show that the non-resonant emission is fundamentally related to the total absorption cross-section of a material through an inverse relation. This will be proven by extension of the general theory of fluorescence yield for the case of a thick, homogeneous specimen. We will also demonstrate the utility of IPFY with measurements of NiO, NdGaO₃, LNSCO, and stainless steel 304 at soft and intermediate x-ray energies. These experiments will highlight some essential features of IPFY spectroscopy and demonstrate how it can be an invaluable tool when the other experimental techniques fail to provide reliable spectra. We will also demonstrate how one can exploit the geometry dependence of IPFY to quantitatively determine the composition of a sample and the total x-ray absorption coefficient. Additionally, we will consider the special cases of multilayers and powder specimens, where the theory of fluorescence yield requires approximations and is not as well-behaved as in thick, homogenous specimens. Ultimately, these experiments and theoretical developments will be used to support the claim that IPFY is a bulk sensitive measure of the total x-ray absorption coefficient. Moreover, we will show that IPFY is not affected by saturation effects, is insensitive to surface contamination layers and provides reliable spectra even for strongly insulating materials. These properties make IPFY a suitable spectroscopic technique for studying XAS in a wide range of materials.

Despite previous extensive study of the widely-employed ruthenium-catalysed olefin metathesis reaction, the finer mechanistic details have not been elucidated. An area that is noticeably lacking is spectroscopic exploration of the relevant complexes. In this work, organometallic ruthenium complexes of importance to olefin metathesis have been investigated using Ru K-edge X-ray absorption spectroscopy. The lowest energy feature in the Ru K-edge spectrum has been unambiguously assigned as due to Ru 4d←1s transitions. These electric-dipole-forbidden transitions are extremely sensitive to geometry. For centrosymmetric complexes, the pre-edge feature has very low intensity because it is limited by the weak electric quadrupole mechanism. By contrast, non-centrosymmetric complexes exhibit a substantial increase in pre-edge intensity because Ru 5p-4d mixing introduces electric-dipole-allowed character to the Ru 4d←1s transitions. The energy of the edge feature in the Ru K-edge spectrum corresponds to ionisation of 1s electrons and is a good indicator of the charge on the metal centre. Unexpectedly, we found that the first-generation (L = PCy₃) Grubbs precatalyst (1) has a higher 1s ionisation energy than the second-generation (L = H₂IMes) complex (2). This effect provides a compelling rationale for the unexplained differences in phosphine dissociation kinetics for complexes 1 and 2: the phosphine dissociation rate of 2 is slower than 1 because the metal centre is more electron-deficient in 2. Density functional theory calculations confirm the charge differences and offer some insight into the nature of bonding in these complexes, particularly with regard to the N-heterocyclic carbene and trialkylphosphine ligands. On the basis of these results, we propose that, for this system, the NHC ligand is a weaker σ-charge donor than the phosphine ligand, and that the NHC accepts significant π-electron density from the metal; both interactions function to reduce the electron density on the ruthenium centre. An ultimate goal is to investigate reactive species in the olefin metathesis mechanism; accordingly, we have made considerable progress toward collecting XAS data for a metallacyclobutane species, and we are pursuing methods to trap the four-coordinate intermediate in the metathesis cycle.

Despite previous extensive study of the widely-employed ruthenium-catalysed olefin metathesis reaction, the finer mechanistic details have not been elucidated. An area that is noticeably lacking is spectroscopic exploration of the relevant complexes. In this work, organometallic ruthenium complexes of importance to olefin metathesis have been investigated using Ru K-edge X-ray absorption spectroscopy. The lowest energy feature in the Ru K-edge spectrum has been unambiguously assigned as due to Ru 4d←1s transitions. These electric-dipole-forbidden transitions are extremely sensitive to geometry. For centrosymmetric complexes, the pre-edge feature has very low intensity because it is limited by the weak electric quadrupole mechanism. By contrast, non-centrosymmetric complexes exhibit a substantial increase in pre-edge intensity because Ru 5p-4d mixing introduces electric-dipole-allowed character to the Ru 4d←1s transitions. The energy of the edge feature in the Ru K-edge spectrum corresponds to ionisation of 1s electrons and is a good indicator of the charge on the metal centre. Unexpectedly, we found that the first-generation (L = PCy₃) Grubbs precatalyst (1) has a higher 1s ionisation energy than the second-generation (L = H₂IMes) complex (2). This effect provides a compelling rationale for the unexplained differences in phosphine dissociation kinetics for complexes 1 and 2: the phosphine dissociation rate of 2 is slower than 1 because the metal centre is more electron-deficient in 2. Density functional theory calculations confirm the charge differences and offer some insight into the nature of bonding in these complexes, particularly with regard to the N-heterocyclic carbene and trialkylphosphine ligands. On the basis of these results, we propose that, for this system, the NHC ligand is a weaker σ-charge donor than the phosphine ligand, and that the NHC accepts significant π-electron density from the metal; both interactions function to reduce the electron density on the ruthenium centre. An ultimate goal is to investigate reactive species in the olefin metathesis mechanism; accordingly, we have made considerable progress toward collecting XAS data for a metallacyclobutane species, and we are pursuing methods to trap the four-coordinate intermediate in the metathesis cycle. / Science, Faculty of / Chemistry, Department of / Graduate

The alkylation of pyrimidyl aldehyde by diisopropylzinc has received immense attention over the last decade. This is mainly because the reaction which was discovered by Soai and coworkers is capable of achieving a homochiral product from an essentially achiral precursor. The strong amplification of the enantiomeric excess occurs because of a transition state complex which is responsible for autocatalysis. Clarifying the structural nature of the organometallic species involved in the reaction is vital for understanding the mechanism of the chiral amplification process. Known mechanistic details are patchy and based on studies that address molecular level details by NMR, computational chemistry, calorimetric and kinetic studies. The studies reported in this thesis for the first time directly addressed the nature of the intermediate by structural analysis with X-ray Absorption Fine Structure (XAFS) Spectroscopy at the Zn K-edge. These measurements provide bond distances, local coordination numbers and the geometry of ligands in the local environment around the Zn centres. First, the molecular level origin of the solvent dependencies in the asymmetric amplification by the Soai process is elucidated. A rationale for the behaviour of dialkylzinc compounds in polar and non-polar solvents is reported. Structural causes for often observed chirality depletion in polar solvents are elucidated. Further studies then examined the nature of the products formed by the reaction of various chiral ligands and dialkylzinc compounds. Different chiral ligands are examined and the complex structure was determined.Finally, first results of in situ studies of the reaction progress in continuous flow channel cells are reported.

El objetivo de esta tesis es estudiar la agrupación y el crecimiento de especies metálicas confinadas o soportadas en materiales porosos mediante espectroscopia de absorción de rayos X in situ. Para lograrlo, las especies de paladio y plata se han introducido en materiales porosos (¿-alúmina, carbón activo y zeolitas) mediante impregnación vía húmeda y métodos de intercambio iónico, respectivamente. Luego, el agrupamiento de estas especies metálicas se ha controlado mediante tratamientos de activación en diferentes atmósferas (inerte, oxidativa y reductiva) y seguido por XAS de manera detallada. El objetivo principal del trabajo actual es demostrar que tanto XANES como EXAFS pueden proporcionar información valiosa y, en cierto punto, innovadora durante el control de especies metálicas (en términos de tipo y tamaño de las especies). Aprovechando los procedimientos de análisis inusuales, como el análisis de los cumulantes, el ajuste de la parte imaginaria de la transformada de Fourier y otros, es posible obtener información refinada sobre los sistemas investigados. En la sección de introducción, se proporciona una compilación de estudios en los que se ha utilizado XAS como técnica importante para caracterizar especies metálicas en materiales porosos. Conscientes de que las personas pueden usar dicha introducción como base para estudios más complejos en el futuro, la discusión se ha dirigido tentativamente hacia este objetivo. El capítulo 4 se centra en el estudio de la influencia de los precursores de paladio y la naturaleza del soporte en las nanopartículas resultantes. El proceso de activación completo, es decir, la transformación precursor --> nanopartícula, ha sido seguido por XAS in situ. El análisis estuvo compuesto por el punto de partida (material impregnado), calcinación en flujo de O2 y reducción posterior con H2. La consecuencia del uso de diferentes precursores metálicos y soportes se ha discutido en términos del número de coordinación promedio obtenido a partir del análisis de datos de EXAFS, que fue respaldado por técnicas de caracterización de laboratorio. El capítulo 5 está dedicado al estudio de la agrupación de plata durante y después de los tratamientos de activación utilizando zeolitas de poro pequeño intercambiadas con plata como precursores y nanocontenedores. Se ha estudiado la influencia de la estructura y la composición química de los materiales basados en plata sobre las especies metálicas formadas en diferentes condiciones de agrupamiento y redispersión del metal (calcinación usando atmósferas distintas, reducción en H2, redispersión en O2) utilizando métodos de caracterización in situ o ex situ. Después, se discuten las consecuencias catalíticas de las zeolitas que contienen Ag en la reacción de SCO-NH3. En esta sección, la combinación de XAS in situ con varias técnicas de laboratorio ha demostrado ser fundamental para un completo entendimiento del trabajo. Finalmente, una lista de proyectos desarrollados en paralelo a esta tesis se proporciona al final de este documento. / The aim of this thesis is to study the clustering and growth of metallic species either confined or supported in porous materials by in situ X-ray absorption spectroscopy. To accomplish this task, palladium and silver species were introduced into porous materials (¿-alumina, activated carbon and zeolites) by wetness impregnation and ion-exchange methods, respectively. Then, the clustering of these metallic species was controlled by activation treatments in different atmospheres (inert, oxidative and reductive) and followed by XAS in a comprehensive way. The principal goal of current work is to demonstrate that both XANES and EXAFS can provide valuable and, at certain point, innovative information during tuning of metallic species (in terms of type and size). Taking advantage of unusual analysis procedures, such as cumulant approach, fitting of imaginary part of Fourier transform and others, it is possible to obtain refined information about the investigated systems. In the introduction section, a compilation of studies in which XAS was used as important technique to characterize metallic species in porous materials is provided. Conscious that people can use such introduction as a basis for more complex studies in the future, the discussion has been tentatively directed toward this goal. The chapter 4 is focused on the study of the influence of palladium precursors and the nature of support on the resultant nanoparticles. The whole activation process, i.e. the transformation precursor --> nanoparticle, was followed in situ by XAS. The analysis pathway was composed by the starting point (as-impregnated), calcination in O2 flow and posterior reduction with H2. The consequence of using distinct metal precursors and supports were discussed in terms of average coordination number obtained from EXAFS data analysis, which was co-supported by laboratory characterization techniques. The chapter 5 is dedicated to the study of silver clustering during and after activation treatments using Ag-containing small-pore zeolites as precursors and nanocontainers. The influence of framework structure and chemical composition of Ag-based materials on formed Ag species at different clustering and metal redispersion conditions (calcination using distinct atmospheres, reduction in H2, redispersion in O2) were studied using either in situ or ex situ characterization methods. After, the catalytic consequences of tuned Ag-containing zeolites in SCO-NH3 are discussed. In this section, the combination of in situ XAS with several laboratory techniques proved to be pivotal to have a full picture of the investigated system. Finally, a list of projects developed in parallel to this thesis is provided at the end of this document. / L'objectiu d'aquesta tesi és estudiar l'agrupació i el creixement d'espècies metàl·liques confinades o suportades en materials porosos mitjançant espectroscòpia d'absorció de raigs X in situ. Per a això, les espècies de pal·ladi i plata s'han introduït en materials porosos (¿-alúmina, carbó activat i zeolites) per mitjà de la impregnació via humida i mètodes d'intercanvi iònic, respectivament. Una vegada preparats els materials, l'agrupament de les espècies metàl·liques s'ha controlat fent ús de tractaments d'activació en diferents atmosferes (inert, oxidant i reductora) s'ha estudiat exhaustivament per XAS. L'objectiu principal del treball és demostrar que tant el XANES com l'EXAFS proporcionen informació rellevant i, en certa manera, innovadora per al control d'espècies metàl·liques (en termes de tipus i grandària d'aquestes espècies). Fent ús de procediments de tractament de dades no molt habituals com l'anàlisi de cumulants, l'ajust de la part imaginària de la transformada de Fourier i altres, és possible obtenir informació detallada sobre els sistemes estudiats. En l'apartat de la introducció, es proporciona una recopilació d'estudis en els quals s'ha utilitzat XAS com a tècnica principal per a caracteritzar les anomenades espècies metàl·liques en materials porosos. Aquesta introducció ha estat redactada per a que puga servir com a punt de partida per a futurs estudis que requereixen la utilització de XAS per a la caracterització de les espècies metàl·liques presents en els catalitzadors. El capítol 4 es centra en l'estudi de la influència dels precursors de pal·ladi i la naturalesa del suport front a les nanopartícules resultants. El procés d'activació, és a dir, la transformació precursor --> nanopartícula, ha sigut estudiat per XAS in situ. L'anàlisi per XAS va comprendre els següents passos: punt de partida (material impregnat), calcinació en flux d'O2 i reducció posterior amb H2. La utilització de diferents precursors i suports metàl·lics ha permès dur a terme una discussió, referent al nombre de coordinació mitjà obtingut a partir de l'anàlisi de dades de la zona EXAFS, que ha estat recolzat per altres tècniques de caracterització. El capítol 5 s'ha dedicat a l'estudi de l'agrupació de plata intercanviada en els catalitzadors durant i després dels tractaments d'activació. S'han utilitzat zeolites de porus xicotet, com la CHA i RHO, intercanviades amb plata. L'estudi de la influència de l'estructura zeolítica i la composició química dels materials enfront dels diferents tractaments d'activació (calcinació utilitzant diferents atmosferes, reducció en presència d'H2, re-dispersió en atmosfera d'O2) es va realitzar fent ús de mètodes de caracterització in situ o ex situ. A continuació, es discuteix la influència d'aquestes espècies metàl·liques formades, utilitzant els diferents mètodes d'activació, per a la reacció d'SCO-NH3. En aquest sentit, s'ha demostrat que la combinació de XAS in situ amb diverses tècniques habituals de laboratori és fonamental per al desenvolupament d'aquest treball. Finalment, es presenta una llista de projectes, en els quals també s'ha treballat paral·lelament, on s'ha utilitzat XAS com a tècnica de caracterització. / Wittee Lopes, C. (2018). Characterization of metallic species on porous materials by in situ XAS [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/107953

Nuclear energy can be used to reliably generate large quantities of electricity while providing minimal lifetime CO2 emissions. Given the extreme importance of safety in the nuclear industry, it is necessary to have a fundamental understanding of the materials used throughout the nuclear fuel cycle. It is of particular to importance to develop an understanding of these materials at an atomic level. In this thesis, X-ray absorption spectroscopy (XAS), along with several other X-ray based techniques, has been used to study materials that are produced or proposed for use in the nuclear fuel cycle. Uranium mining and milling operations generate large quantities of waste, known as mine and mill tailings. At their McClean Facility in Northern Saskatchewan, AREVA Resources Canada disposes of the tailings waste using the JEB Tailings Management Facility (TMF). AREVA monitors the mineralization of elements of concern (i.e., Ni, As, Fe, Mo, Ra, and U) within the TMF as part of its on-going commitment towards managing the facility’s environmental impact. Molybdenum (Mo) is predicted to mineralize as insoluble powellite (CaMoO4) within the TMF. However, no experimental evidence confirmed the presence of powellite in the TMF. In Chapter 2, the presence of powellite, and other Mo-bearing minerals, was determined using powder X-ray diffraction (XRD), X-ray fluorescence imaging, and Mo K-edge XAS. The results of this study confirmed that powellite was present in the TMF and showed that Mo K-edge XAS was the only effective way to detect the Mo minerals within the TMF. New materials for use as nuclear fuels were also investigated in this thesis. Spent nuclear fuel must be securely stored for long periods of time due to the presence transuranic elements (TRU; i.e., Pu, Am, Np, Cm), and the use of inert matrix fuels (IMF), which consist of actinides embedded in a neutron transparent (inert) material, have been proposed for to “burn-up” or transmute these TRU species. Stabilized ZrO2 materials have been proposed for use in IMF applications, and in Chapter 3 the thermal stability of a series of NdxYyZr1-x-yO2-\delta materials made by a ceramic synthetic route have been studied using powder XRD, scanning electron microscopy (SEM), and X-ray absorption spectroscopy. (Nd was used as a surrogate for Am.) The results of this study showed that the fluorite structure of the NdxYyZr1-x-yO2- \delta materials was stabilized when y >= 0.05, and that the local environment around Zr was independent of composition or annealing temperature. The effect of synthetic method on the thermal stability of the NdxYyZr1-x-yO2-\delta materials was also determined, and this is the subject of Chapter 4. In this study a series of NdxY0.25-xZr0.75O1.88 materials were synthesized using a low-temperature co precipitation synthesis, and these then annealed at 1400 °C and 1500 °C. The as-synthesized and annealed materials were characterized by powder XRD, SEM, and XAS. This study confirmed that the thermal stability of the materials was dependent on synthetic method, and that materials made using a solid-state method were superior to those produced by a solution-based approach. Y-stabilized zirconia has a low thermal conductivity, which is not ideal for a nuclear fuel. The thermal conductivity could be increased if a lighter cation, such as Sc, was used to stabilize the fluorite structure. In Chapter 5, the thermal stability of a series of NdxScyZr1-x-yO2-\delta materials was investigated. The as-synthesized and annealed materials were studied by powder XRD, SEM, and XAS. These results showed that the fluorite structure was only stable in the annealed materials when x+y >= 0.15 and y >= 0.10. The results of this study provided insight into the possible use of scandia-stabilized zirconia for use as an inert matrix fuel. This studies presented in this thesis have used X-ray absorption spectroscopy and a number of other techniques to characterize materials important to the nuclear fuel cycle. The studies presented here were only possible because of the unique information that can be obtained using XAS. This thesis serves to highlight the importance of XAS as a technique and how it can be applied to solve problems related to the material science of the nuclear fuel cycle.

Understanding the fundamental electronic properties of materials is a key step to develop innovations in many fields of technology. For example, this has allowed to design molecular based devices like organic field effect transistors, organic solar cells and molecular switches. In this thesis, the properties of advanced functional materials, in particular metal-organic molecules and molecular building blocks of 2D materials, are investigated by means of Density Functional Theory (DFT), the GW approximation (GWA) and the Bethe-Salpeter equation (BSE), also in conjunction with experimental studies. The main focus is on calculations aiming to understand spectroscopic results. In detail, the molecular architectures of lutetium-bis-phthalocyanine (LuPc2) on clean and hydrogenated vicinal Si(100)2×1, and of the biphenylene molecule on Cu(111) were analysed by means of X-ray Photoelectron spectroscopy (XPS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy; DFT calculations were performed to obtain insights into the atomic and electronic structures. Furthermore, detailed information about the electronic states of the gas phase iron phthalocyanine (FePc) and of the gas phase biphenylene molecule were obtained through XPS and NEXAFS spectroscopy. I have studied by means of DFT, multiplet and GWA calculations the electronic correlation effects in these systems. Also the optical, electronic and excitonic properties of a hypothetical 2D material based on the biphenylene molecule were investigated by GWA and BSE calculations. Monolayers of metal-free phthalocyanine (H2Pc) on Au(111) and of FePc on Au(111) and Cu(100)c(2×2)-2N/Cu(111) with and without pyridine modifier were studied by XPS and final state calculations. A multiplet approach to compute L-edges employing the hybridizations function, known from dynamical mean field theory, was proposed and applied to transition metal oxides.

Diluted magnetic semiconductor oxides (DMSOs) have received great attention recently due to their outstanding applications in optoelectronic and spintronic devices. Ever since the initial observation of ferromagnetism at room temperature in cobalt-doped titania, extensive effort is concentrated on preparation of transition metal doped wide band gap semiconductors, especially Mn- doped ZnO. Compared to Mn-doped ZnO, magnetic interactions in SnO! and In!O! semiconductors have been underexplored. SnO! and In!O! semiconductors have many applications, owing to their high charge carrier density and mobility as well as high optical transparency. Investigation on electronic structure changes induced by dopants during the synthesis procedure can effectively influence magnetic interactions between charge carriers. In this work, a combination of structural and spectroscopic methods was used to probe as-synthesized SnO! and In!O! nanocrystals doped with Mn!! and Mn!! as precursors. X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy are powerful techniques to explore formal oxidation state of manganese dopant, electronic environment, number of nearest neighbors around the absorbent, and bond lengths to the neighboring atoms. Analysis reveals the presence of multiple oxidation states in the doped nanocrystals, and establishes a relation between !"!! ratio and expansion or contraction of lattice parameters. !"!! Although doping semiconductors are crucial for manipulating the functional properties, the influence of dopants on nanocrystals structure is not well understood. Nanocrystalline films prepared from colloidal Mn-doped SnO! and In!O! nanocrystals through spin coating process exhibit ferromagnetic behavior in temperatures ranging from 5 K to 300 K. Magnetic transformation from paramagnetic in free-standing Mn-doped nanocrystals to strong ferromagnetic ordering in nanocrystalline films is attributed to the formation of extended structural defects, e.g., oxygen vacancies at the nanocrystals interface. Magnetic circular dichroism (MCD) studies clearly show that Mn!! occupies different symmetry sites in indium oxide, when bixbyite and rhombohedral In!O! nanocrystals (NCs) are compared.