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

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

Carboxylic acids have played an important role in the field of actinide (An) and lanthanide (Ln) separations and the reprocessing of irradiated nuclear fuel. Recent bench-scale experiments have demonstrated that 3-carboxy-3-hydroxypentanedioic acid (citric acid) is a promising aqueous complexant that can effectively aid in the separation of transition metals from f-element mixtures. Furthermore, citric acid was found to be a suitable buffer for the nitrogen donating ligand diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA) which has a higher complexation affinity for An over Ln. The complexation of Ln and An with anions of citric acid and DTPA have been previously studied with conflicting results regarding the coordination of metal ions between carboxylic groups, the feasibility of protonated metal complexes, and the formation constants themselves. Using potentiometry, spectrophotometry,microcalorimetry, and specific ion interaction modeling, we investigated metal complexes of citric acid and DTPA with selected trivalent and tetravalent Ln and An ions. The complexes were investigated with respects to stability constants, thermodynamics of complexation, oxidation states, the concentration of electrolyte, ligand size, thermodynamics of complexation, oxidation states, the concentration of electrolyte, ligand size, and metal ionic radius. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Jan. 3, 2013 - July 3, 2013

Structures as determined by single crystal X-ray methods for lanthanoid(III) compounds for series of simple homoleptic species with diverse ligands frequently display variations entailing a diminution in coordination number (‘C.N.’), a consequence of the variation in the size of the atoms/ions due to the ‘lanthanoid contraction’. A change from C.N. nine to eight is common, clearly separating compounds of the light/‘early’ or heavy/‘later’ metal atoms. Earlier work on the complexes of the lanthanoid(III) picrates arose out of the exploration of simple reagents which might usefully exploit lanthanoid ion properties for purposes such as solvent extraction. They are also of potential synthetic utility because of their relatively high solubility in apolar solvents. This thesis encompasses a systematic structural study of hydrated lanthanoid picrate complexes (including those of yttrium) with a selection of dipolar aprotic solvent ligands, namely trimethylphosphate (‘tmp’), dimethylsulfoxide (‘dmso’), hexamethylphosphoramide (‘hmpa’), N,N´-dimethylacetamide (‘dma’), N-methylpyrrolidinone (‘nmp’) and octamethylpyrophosphoramide (‘ompa’), all liquids at room temperature and all unidentate, with the exception of ompa which can be considered in some cases to behave as the equivalent of two unidentate ligands, in others as a chelate. Structures of adducts of these ligands with scandium picrate are also included in order to gain further insight into the coordination behavior of the totality of the group ‘3’ transition metals, and, for similar reasons, a study of the structures of complexes of Eu(dipivaloylmethanide)3 with the same (solvent) ligands as a ‘baseline’. In the course of these studies, hydrolysis of the aprotic solvent trimethylphosphate was found to lead to novel adducts of the dimethylphosphate (‘dmp’) ligand; the introduction of polycyclic aromatic nitrogen base ligand complexes resulted in further novel mixed ligand compounds, supplemented by a study of protonated base picrate salts. This work aims not only to establish structural ‘domains of existence’ with a concomitant consideration of the associated stereochemistry for these related series of rare earth complexes, but, also, to enhance our understanding of metal ion solvation and the interactions of aromatic groups within these types of crystal structures.

Thesis (Ph.D.)--McMaster University (Canada), 1990. / Source: Dissertation Abstracts International, Volume: 62-13, Section: A, page: 0000.

Thesis (Ph. D.) --Memorial University of Newfoundland, 1997. / Restricted until November 1998. Bibliography: leaves 264-281.