Orientador: Sergio Antonio Marques de Lima / Banca: Ana Maria Pires / Banca: Alexandre de Oliveira Legendre / Resumo: Íons lantanídeos são utilizados como centros emissores em dispositivos emissores de luz, apresentam alta eficiência de emissão, porém baixa absortividade molar. Este problema pode ser contornado com o uso de ligantes orgânicos com alta absortividade e que transfiram energia de forma eficiente para os íons lantanídeos em complexos. A transferência de energia dos estados singlete e triplete do ligante orgânico para o íon emissor recebe o nome de efeito antena. Os complexos de irídio apresentam alta absortividade molar e um estado excitado, que é uma mistura do estado excitado do ligante com uma banda de transferência de carga metal ligante (3L-TCML) e que pode transferir energia de forma eficiente para os íons lantanídeos. Desta forma, os compostos multicentrados heteronucleares de íons lantanídeos ligados a complexos de irídio por um ligante que faça a ponte entre os centros metálicos podem produzir um efeito "super-antena" aumentando a eficiência de emissão nos íons lantanídeos. No trabalho desenvolvido foram realizadas sínteses e caracterizações de complexos mononucleares contendo íons Ir3+ e Eu3+, e também complexos bimetálicos tetranucleares ligados em ponte. A caracterização dos complexos foi realizada através das espectroscopias de absorção no infravermelho e UV-Vis e espectroscopia de fotoluminescência. Os espectros de fotoluminescência dos compostos mononucleares sintetizados mostram características semelhantes às encontradas na literatura, enquanto nos complexos heterobimetálicos, inéditos até o presente momento, a emissão é característica tanto dos complexos de Ir3+ quanto do íon Eu3+, indicando que houve a ligação em ponte entre os complexos, no entanto, a transferência de energia não é eficiente entre os estados excitados 3L-TCML e o estado emissor do lantanídeo. Isso ocorre devido à aproximação energética entre esses níveis o que favorece um processo de retro doação ... / Abstract: Lanthanides ions are widely used as emitting centers in light emitting devices. They hold high efficiency of emission, but low molar absorption. This problem can be overcome by the use of organic ligands that show highest molar absorbance and are able to transfer the energy of their excited state to the emitting states of the lanthanide ions. The energy transfer from the triplet and singlet levels of organic ligand to the lanthanide ion is called "antenna effect". Iridium complexes hold high molar absorption and an excited state that is a mix of ligand triplet-excited state and a charge-transfer metal to ligand band (3L-MLCT); this energy level can transfer energy efficiently to the lanthanide ions. Therefore, heteronuclear compounds multicentered of lanthanide ions bonded in bridge with iridium complexes by a ligand that connects the two metallic centers can produce a "super-antenna" effect, increasing the emission efficiency in the lanthanide ions. In this study, we synthesized and characterized mononuclear complexes containing Ir3+ and Eu3+ ions, and bimetallic tetranuclear complexes (Ir3+-Eu3+). These complexes were characterized by infrared absorption spectroscopy, UV-Visible absorption spectroscopy and photoluminescence spectroscopy. The photoluminescence spectra of the mononuclear compounds showed similar characteristics to those encountered in the literature, whereas the heterobimetallic complexes exhibit emission characteristic of both, Ir3+ complexes and Eu3+ complexes. This suggests that the bond in bridge between the metallic centers did happened, and the energy was transferred from the excited state 3L-MLCT to the emitting state of the lanthanide, but this was not very efficient. This may occurs probably by an approximation between the energy levels that favors a backdonation process. Geometry and UV-Vis spectra were simulated using quantum software, finding high agreement between the theory and experimental data / Mestre

Orientador: Massao Ionashiro / Banca: Adelino Vieira de Godoy Netto / Banca: Lazaro Moscardini D'Assunção / Banca: Glimaldo Marino / Banca: Roni Antonio Mendes / Resumo: Foram sintetizados, no estado sólido, os compostos Ln2L3∙nH2O, sendo que Ln representa os lantanídeos trivalentes (La ao Lu) e o ítrio(III) e o L representa o succinato (C4H4O4). Os compostos foram sintetizados por adição estequiométrica, sob agitação, do ligante nas respectivas soluções de cloretos ou nitratos de lantanídeos. A caracterização dos compostos foi realizada utilizando métodos como difratometria de raios X pelo método do pó, análise elementar, complexometria e as técnicas termoanalíticas como termogravimetria e análise térmica diferencial simultânea (TG-DTA), caloria exploratória diferencial (DSC) e termogravimetria acoplada à espectroscopia de absorção na região do infravermelho com transformada de Fourier (TG-FTIR). Os resultados forneceram informações sobre o comportamento térmico, cristalinidade, estequiometria dos compostos estudados. Também foi possível identificar os produtos gasosos liberados durante o aquecimento / Abstract: Solid-state Ln2L3∙nH2O compounds, where Ln stands for trivalent lanthanides (La to Lu) or yttrium(III) and L is succinate(C4H4O4), have been synthesized. The solid-state compounds were prepared by stoichiometric relation adding slowly, with continuous stirring the ligand solution to the respective metal chloride or nitrate solution. The characterization of the compounds was performed using X-ray powder diffratometry, elemental analysis,complexometry, simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC) and thermogravimetry coupled to absorption spectroscopy in the region of infrared with Fourier transform (TG-FTIR). The results provided information about thermal behaviour, crystallinity, stoichiometry of the compounds studied. It was also possible to identify the gaseous products released during heating / Doutor

Within solid-state chemistry, coordination polymers have gained interest for use in various applications such as sensing, catalysis, display technology, hydrogen storage, etc. The use of lanthanide ions in these materials provides a mean of exploring how structure may affect luminescence efficiency. In this study, the photophysics of several lanthanide benzenecarboxylates was studied. This data combined with data from other coordination polymers created in our lab indicate that the established guidelines for producing highly efficient materials may not correlate directly from solution to the solid state and that structure may also play a role. / by Jessica Montressa Clark. / Thesis (M.S.)--Florida Atlantic University, 2013. / Includes bibliography. / Mode of access: World Wide Web. / System requirements: Adobe Reader.

The organic linker 1,2,4,5-benzenetetracarboxylic acid (BTC) has been widely used in the construction of lanthanide metal-organic frameworks (MOFs) due the high symmetry and versatile nature of its structure. Under identical hydrothermal reaction conditions, it was discovered that lanthanide BTC MOFs will form one of four unique structures based on its location in the series (La-Sm, Eu-Tb, Dy-Tm, Yb-Lu). This is uncommon in LOF materials, as in many cases the same compound can be produced for all of the lanthanides or two different structures may be observed for the first and second half of the series. Descriptions and comparisons of these structures as discussed herein, noticeably the decrease in coordination number and the lanthanide-oxygen bond lengths as the lanthanide atomic number increases. This thesis also attempts to use these compounds to catalyze a model mixed-aldol reaction. Two closely related BTC compounds from yttrium and uranium are also presented. The structure of the yttrium BTC MOFs was identical to that of the Eu, Gd and Tb compounds. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2015. / FAU Electronic Theses and Dissertations Collection

by Chan Hoi Shan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2000. / Includes bibliographical references (leaves 111-119). / Abstracts in English and Chinese. / Acknowledgement --- p.iii / Abbreviation --- p.iv / List of Compounds --- p.vi / Abstract --- p.vii / Abstract (Chinese) --- p.ix / Chapter Chapter 1. --- Introduction / Chapter 1.1 --- Lanthanide-Amine Compounds --- p.1 / Chapter 1.2 --- Lanthanide-Amide Compounds --- p.3 / Chapter 1.3 --- Lanthanide-Imide Compounds --- p.11 / Chapter 1.4 --- Some Applications of Lanthanide-Amide Compounds in Organic Synthesis --- p.15 / Chapter 1.5 --- Aims --- p.19 / Chapter Chapter 2. --- Synthesis and Structural Characterization of Anionic and Neutral Dichlorolanthanocene Compounds / Chapter 2.1 --- Synthesis --- p.20 / Chapter 2.2 --- Structural Characterization --- p.22 / Chapter 2.3 --- Conclusion --- p.23 / Chapter Chapter 3. --- Synthesis and Structural Characterization of Amido-Lanthanide Compounds / Chapter 3.1 --- Synthesis and Structural Characterization of Yb(NHAr)3(THF)n --- p.26 / Chapter 3.2 --- "Synthesis and Structural Characterization of Yb(NHC6H3iPr2- 2,6)4Na(THF)" --- p.38 / Chapter 3.3 --- "Synthesis and Structural Characterization of Yb(Cp"")(NHAr)2(L)" --- p.45 / Chapter 3.4 --- "Synthesis and Structural Characterization of Yb(Cp"")(NHC6H3iPr2- 2,6)3M(L)" --- p.54 / Chapter 3.5 --- Synthesis and Structural Characterization of Yb(NHAr)3(NH2Ar)(L) --- p.74 / Chapter 3.6 --- Conclusion --- p.76 / Chapter Chapter 4. --- Synthesis and Structural Characterization of Imido-Lanthanide Compounds / Chapter 4.1 --- Synthesis --- p.81 / Chapter 4.2 --- Structural Characterization --- p.82 / Chapter 4.3 --- Conclusion --- p.85 / Chapter Chapter 5. --- Summary and Remarks / Chapter 5.1 --- Summary --- p.96 / Chapter 5.2 --- Remarks --- p.97 / Chapter Chapter 6. --- Experimental Section --- p.98 / References --- p.111 / Appendix --- p.120

With the increase of the the global energy consumption has also been increasing, which is about 18 TW nowadays (Dudley, 2018), the anthropogenic CO2 emissions have also been increasing, which is about 410 ppm nowadays (Dudley, 2018; Tans & Keeling, 2019). Numerous evidences have been reported indicating that high atmospheric CO2 concentration can have significant greenhouse effect and thus lead to global warming and climate change (Pachauri et al, 2014; Hansen et al, 2013). Therefore, measures need to be taken to control and reduce the atmospheric CO2 concentration. In such circumstance, carbon capture, utilization and storage (CCUS) technologies have been proposed and developed to close the carbon cycle. Mineral carbonation (MC) is one of the CCUS technologies, which mimics the natural silicate weathering process to react CO2 with silicate materials so that carbon can be stabilized in the form of insoluble carbonates for permanent carbon storage (Seifritz, 1990; Lackner et al, 1995). Both Ca- or Mg-bearing silicate minerals and alkaline silicate industrial wastes can be employed as the feedstock for mineral carbonation (Sanna et al, 2014; Gadikota et al, 2014; Park, 2005; Park & Fan, 2004; Park et al, 2003; Park & Zhou, 2017; Zhou, 2014; Zhao, 2014; Swanson, 2014). While they share similar chemistries and total Mg and Ca contents, different MC feedstock can lead to different challenges for CCUS. As for silicate minerals, although they have large enough capacity to mineralize all the anthropogenic CO2 emissions, their reactivities are generally very low, and measures should be developed to accelerate the carbonation kinetics of the minerals (Sanna et al, 2014). However, the elemental extraction of the silicate minerals is a relatively complicated kinetic process, because silica-rich passivation layer can form on the particle surface during mineral dissolution process and thus the rate-limiting step of the process can change from chemical reaction to mass transfer. Without a clear understanding of the elemental extraction kinetics, the design and evaluation of different acceleration methods aiming at different rate-limiting steps of the process can be challenging. As for alkaline industrial wastes, they are generally more reactive than silicate minerals, but can be more heterogeneous with more complicated compositions. In such cases, the separation and recovery of other elements should also be integrated with the carbonation process so that the overall sustainability of the mineral carbonation technology can be enhanced. In order to address these challenges, this study focused on the fundamental understanding of dissolution and carbonation behaviors of alkaline silicate materials and integration of step-wise separations of rare-earth elements (REEs). Both experimental and modeling studies were carried out to provide insights into how Mg and Ca as well as REEs are leaching into solvents at different conditions, and the fundamental understandings on mineral dissolution kinetics and mechanisms were also put forward. The fate of REEs in different product streams was also identified, and methods were developed and optimized to recover and concentrate REEs, while producing solid carbonates with highest purities. Hopefully, the findings in this study can not only advance the carbon mineralization technology but also contribute to the utilization and extraction of alkaline metals, as well as REEs, from other complex unconventional resources for the sustainable energy and material future.

by Kui Chi Fai. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references. / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstracts --- p.ii / Table of Contents --- p.v / Abbreviations --- p.viii / Chapter CHAPTER 1. --- METALLATION OF AMINOPYRIDINE AND AMINOQUINOLINE / Chapter 1.1 --- INTRODUCTION --- p.1 / Chapter 1.1.1 --- General Background --- p.1 / Chapter 1.1.2 --- A Brief Review on Sodium and Potassium Amides --- p.3 / Chapter 1.1.3 --- Preparation of Sodium and Potassium Amides --- p.8 / Chapter 1.2 --- RESULTS AND DISCUSSION --- p.10 / Chapter 1.2.1 --- "Synthesis of [NH(SiButMe2)(R)] [ R = 2-C5H3N-6-Me, 8-C9H6N ] as Ligand Precursors" --- p.10 / Chapter 1.2.2 --- Synthesis of Sodium and Potassium Amido Complexes Containing the Pyridine-Functionalized Amido Ligand [N(SiButMe2)(2-C5H3N-6-Me)]- --- p.11 / Chapter 1.2.2.1 --- Sodium Pyridyl Amido Complexes --- p.11 / Chapter 1.2.2.2 --- Potassium Pyridyl Amido Complexes --- p.12 / Chapter 1.2.3 --- Synthesis of Sodium and Potassium Amido Complexes Containing the Quinoline-Functionalized Amido Ligand [N(SiButMe2)(8-C9H6N)]- --- p.15 / Chapter 1.2.3.1 --- Sodium Quinolyl Amido Complexes --- p.15 / Chapter 1.2.3.2 --- Potassium Quinolyl Amido Complexes --- p.16 / Chapter 1.2.4 --- Physical Characterization of Compounds 3-9 --- p.17 / Chapter 1.2.5 --- "Molecular Structures of Compounds 3, 5 and 7" --- p.20 / Chapter 1.3 --- EXPERIMENTALS FOR CHAPTER 1 --- p.30 / Chapter 1.3 --- REFERENCES FOR CHAPTER 1 --- p.36 / Chapter CHAPTER 2. --- "Synthesis,Structures, and Catalytic Properties of Lanthanide Metal Amides Containing the Pyridine - Functionalized Amido Ligand [N(SiButMe2)(2-C5H3N-6-Me)]-" / Chapter 2.1 --- INTRODUCTION --- p.39 / Chapter 2.1.1 --- General Background --- p.39 / Chapter 2.1.2 --- A Brief Review on Rare Earth Amido Complexes --- p.40 / Chapter 2.1.3 --- General Preparation Methods to Lanthanide Metal Amides --- p.44 / Chapter 2.1.4 --- Ring-Opening Polymerization of Lactones --- p.45 / Chapter 2.1.5 --- Objectives of This Work --- p.48 / Chapter 2.2 --- RESULTS AND DISCUSSION --- p.49 / Chapter 2.2.1 --- Synthesis and Physical Properties --- p.49 / Chapter 2.2.1.1 --- Homoleptic Lanthanide Metal Amides 10-18 --- p.49 / Chapter 2.2.1.2 --- Heteroleptic Lanthanide Metal Amides 19-22 --- p.53 / Chapter 2.2.2 --- Molecular Structures --- p.56 / Chapter 2.2.2.1 --- Molecular Structures of Homoleptic Lanthanide Metal Amides 10-18 --- p.56 / Chapter 2.2.2.2 --- Molecular Structures of Heteroleptic Lanthanide Metal Amides 19-22..… --- p.76 / Chapter 2.2.3 --- Reactivity Studies --- p.89 / Chapter 2.2.3.1 --- "Reaction with 3,5-di-tert-butylcatechol (dbcH2)" --- p.89 / Chapter 2.2.3.2 --- Ring-Opening Polymerization of s-Caprolactone --- p.95 / Chapter 2.3 --- EXPERIMENTALS FOR CHAPTER 2 --- p.100 / Chapter 2.4 --- REFERENCES FOR CHAPTER 2 --- p.108 / Chapter CHAPTER 3. --- Preparation of Pyridine Adducts of Zinc(II) Chloride and Low-coordinate Zinc(II) Dithiolate and Bis(aryloxide) Compounds / Chapter 3.1 --- INTRODUCTION --- p.111 / Chapter 3.1.1 --- General Background --- p.111 / Chapter 3.2 --- RESULTS AND DISCUSSION --- p.115 / Chapter 3.2.1 --- Synthesis of Pyridine Adducts of Zinc(II) Chloride --- p.115 / Chapter 3.2.2 --- Synthesis of Novel Three-Coordinate Zinc(II) Dithiolate and Bis(aryloxide) --- p.116 / Chapter 3.2.3 --- Physical Characterization of Compounds 23-26 --- p.118 / Chapter 3.2.4 --- Molecular Structures of Compounds 23-25 --- p.122 / Chapter 3.3 --- EXPERIMENTALS FOR CHAPTER 3 --- p.129 / Chapter 3.4 --- REFERENCES FOR CHAPTER 3 --- p.133 / Chapter CHAPTER 4. --- Summary of this Research Work --- p.135 / Appendix 1 General Procedures and Physical Measurements --- p.137 / "Appendix 2 Table A-l. Selected Crystallographic Data for Compounds 3, 5，7，10 and 11" --- p.139 / Table A-2. Selected Crystallographic Data for Compounds12-16 --- p.140 / Table A-3. Selected Crystallographic Data for Compounds17-21 --- p.141 / Table A-4. Selected Crystallographic Data for Compounds22-25 --- p.142

Metal oxide thin films are dynamic materials that have revolutionised the nature of semiconductor and electronic thin film devices. Recently, progress has stagnated in some aspects due to the increasingly complex deposition apparatus required, and the dearth of suitable precursor complexes of certain ???difficult??? metals. This thesis seeks to address both of these issues. The application of a precursor complex, Mg6(O2CNEt2)12 to the SSCVD of MgO thin films delivered the highest quality films ever reported with this technique. The resultant films were found to be of purely (111) orientation. Due to the nature of the precursor, the chemical reactions occurring at the surface during SSCVD growth result in a high growth rate, low flux environment and films of (111) orientation have been achieved without the amorphous underlayer. This finding has important implications for buffer layers in perovskite thin film devices. The unprecedented precursor chemistry has been used as a basis for the extremely high quality material produced, along with the unusual, yet beneficial structural morphology it possesses. A new range of barium complexes with single encapsulating ligands have been prepared for use in chemical vapour deposition (CVD) of BaTiO3 thin films. A novel pathway to an unprecedented class of barium carbamates is reported, and also new dianionic bis ??-ketoesterates and their barium, strontium, and calcium analogues were synthesised. High resolution mass spectrometry showed the barium bis ??-ketoesterate derivatives to be monomeric, and preliminary testing indicated some volatility in these species. Insights were gained into the likely successful pathways to building a volatile heterobimetallic precursor complex containing an alkaline earth metal. The knowledge of intimate mixing in heterobimetallic precursor complexes was extended by some novel chemistry to develop the first mixed Zn/Mg carbamato cluster complexes. These complexes were found to be excellent SSCVD precursors for ZnxMg1-xO thin films. Thin films were deposited with these precursors and exhibited a single preferred orientation, with a constant amount of magnesium throughout the bulk of the films. Investigation of the light emission properties of the films revealed significant improvements in the structural order commensurate with the incorporation of magnesium, and the formation of the ZnxMg1-xO alloy.

Metal oxide thin films are dynamic materials that have revolutionised the nature of semiconductor and electronic thin film devices. Recently, progress has stagnated in some aspects due to the increasingly complex deposition apparatus required, and the dearth of suitable precursor complexes of certain ???difficult??? metals. This thesis seeks to address both of these issues. The application of a precursor complex, Mg6(O2CNEt2)12 to the SSCVD of MgO thin films delivered the highest quality films ever reported with this technique. The resultant films were found to be of purely (111) orientation. Due to the nature of the precursor, the chemical reactions occurring at the surface during SSCVD growth result in a high growth rate, low flux environment and films of (111) orientation have been achieved without the amorphous underlayer. This finding has important implications for buffer layers in perovskite thin film devices. The unprecedented precursor chemistry has been used as a basis for the extremely high quality material produced, along with the unusual, yet beneficial structural morphology it possesses. A new range of barium complexes with single encapsulating ligands have been prepared for use in chemical vapour deposition (CVD) of BaTiO3 thin films. A novel pathway to an unprecedented class of barium carbamates is reported, and also new dianionic bis ??-ketoesterates and their barium, strontium, and calcium analogues were synthesised. High resolution mass spectrometry showed the barium bis ??-ketoesterate derivatives to be monomeric, and preliminary testing indicated some volatility in these species. Insights were gained into the likely successful pathways to building a volatile heterobimetallic precursor complex containing an alkaline earth metal. The knowledge of intimate mixing in heterobimetallic precursor complexes was extended by some novel chemistry to develop the first mixed Zn/Mg carbamato cluster complexes. These complexes were found to be excellent SSCVD precursors for ZnxMg1-xO thin films. Thin films were deposited with these precursors and exhibited a single preferred orientation, with a constant amount of magnesium throughout the bulk of the films. Investigation of the light emission properties of the films revealed significant improvements in the structural order commensurate with the incorporation of magnesium, and the formation of the ZnxMg1-xO alloy.

Metal oxide thin films are dynamic materials that have revolutionised the nature of semiconductor and electronic thin film devices. Recently, progress has stagnated in some aspects due to the increasingly complex deposition apparatus required, and the dearth of suitable precursor complexes of certain ???difficult??? metals. This thesis seeks to address both of these issues. The application of a precursor complex, Mg6(O2CNEt2)12 to the SSCVD of MgO thin films delivered the highest quality films ever reported with this technique. The resultant films were found to be of purely (111) orientation. Due to the nature of the precursor, the chemical reactions occurring at the surface during SSCVD growth result in a high growth rate, low flux environment and films of (111) orientation have been achieved without the amorphous underlayer. This finding has important implications for buffer layers in perovskite thin film devices. The unprecedented precursor chemistry has been used as a basis for the extremely high quality material produced, along with the unusual, yet beneficial structural morphology it possesses. A new range of barium complexes with single encapsulating ligands have been prepared for use in chemical vapour deposition (CVD) of BaTiO3 thin films. A novel pathway to an unprecedented class of barium carbamates is reported, and also new dianionic bis ??-ketoesterates and their barium, strontium, and calcium analogues were synthesised. High resolution mass spectrometry showed the barium bis ??-ketoesterate derivatives to be monomeric, and preliminary testing indicated some volatility in these species. Insights were gained into the likely successful pathways to building a volatile heterobimetallic precursor complex containing an alkaline earth metal. The knowledge of intimate mixing in heterobimetallic precursor complexes was extended by some novel chemistry to develop the first mixed Zn/Mg carbamato cluster complexes. These complexes were found to be excellent SSCVD precursors for ZnxMg1-xO thin films. Thin films were deposited with these precursors and exhibited a single preferred orientation, with a constant amount of magnesium throughout the bulk of the films. Investigation of the light emission properties of the films revealed significant improvements in the structural order commensurate with the incorporation of magnesium, and the formation of the ZnxMg1-xO alloy.