1,8-bis(phenylimino)-3,6-ditertbutyl-carbazole is synthesized and characterized, which can be complexed with copper(II) halide by deprotonation and transmetallation. The resulting copper complexes enable to polymerize MMA through RATRP process.

Orientador: Pedro Paulo Corbi / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-25T01:00:34Z (GMT). No. of bitstreams: 1 Paiva_RaphaelEnoqueFerrazde_M.pdf: 15807547 bytes, checksum: e13f0a8a3bbde08ba558ac7cdb13c9a5 (MD5) Previous issue date: 2014 / Resumo: Complexos metálicos têm sido estudados quanto as suas propriedades medicinais há décadas. Neste trabalho, dois complexos inéditos de Ag(I) e Pt(II) foram sintetizados com o anti-inflamatório nimesulida (NMS), e avaliados como agentes antibacterianos e antitumorais. O complexo Ag-NMS (AgC13H11N2O5S) apresenta o ligante em uma coordenação bidentada à prata pelos átomos de N e O do grupo sulfonamida. A estrutura proposta foi confirmada por DFT. Devido à baixa solubilidade em água, foi preparado um complexo de inclusão de Ag-NMS em b-CD, pelo método de co-evaporação. Utilizando o método de Scatchard, foi determinado o valor de Ka = 370 2 L mol. Estudos de RMN por correlação H-H através do espaço mostram que a inclusão ocorre pelo grupo fenoxi da NMS. Já o complexo Pt-NMS (PtC26H22N4O10S2) apresenta dois ligantes, coordenados pelos átomos de N e O do grupo sulfonamida, para cada Pt(II). A DFT indica que o isômero N, O trans é o mais estável. O complexo Ag-NMS apresentou valores de MIC na faixa de 15,0-120 mmol L sobre cepas de Pseudomonas aeruginosa, Escherichia col e Staphylococcus aureus. O CE-[(Ag-NMS)·b-CD], embora mais solúvel em água do que o Ag-NMS, não apresentou atividade antibacteriana nas concentrações testadas. Os complexos Ag-NMS e Pt-NMS mostraram-se citotóxicos sobre células normais (Balb/c 3T3) e tumorais (SK-Mel 103 e Panc-1), porém o Pt-NMS foi significativamente mais seletivo contra as linhagens tumorais. Os ensaios de intercalação com EtBr e a avaliação da estrutura do DNA por dicroísmo circular indicam que o DNA não é um alvo biológico para o complexo Pt-NMS, indicando um mecanismo de ação diferente da cisplatina / Abstract: Metal complexes have been studied regarding its medicinal properties for decades. In this work, novel complexes of Ag(I) and Pt(II) with the anti-inflammatory nimesulide were synthesized and evaluated regarding their antibacterial and antitumoral properties. The Ag-NMS complex (AgC13H11N2O5S) shows the ligand in a bidentate coordination mode, bound to silver through the N and O atoms of the sulfonamide group. The proposed structure was confirmed by DFT. Due to its poor solubility in water, the Ag-NMS complex was included in b-CD, by co-evaporation. The Ka = 370 2 L mol was determined using the Scatchard method. Studies by H-H NMR correlation through space shows the inclusion of NMS by the fenoxi group. The Pt-NMS complex (PtC26H22N4O10S2) contain two ligands, coordinated through the N and O atoms of the sulfonamide group, for each Pt(II). DFT studies indicate that the N,O trans isomer is the most stable. The Ag-NMS complex presents MIC values in the range 15.0-120 mmol L over Pseudomonas aeruginosa, Escherichia coli e Staphylococcus aureus. The inclusion complex CE-[(Ag-NMS)·b-CD], although more soluble in water than Ag-NMS, shows no antibacterial activity in the tested concentrations. Both complexes were cytotoxic against normal (Balb/c 3T3) and tumor (SK-Mel 103 and Panc-1) cells, but the Pt-NMS complex was significantly more selective against tumor cells. The EtBr competitive intercalation assay and the evaluation of CT-DNA structure using circular dichroism show that DNA is not a biological target for the Pt-NMS complex, indicating a mechanism of action different of the cisplatin one / Mestrado / Quimica Inorganica / Mestre em Química

MSc (Chemistry) / Department of Chemistry / See the attached abstract below

The new dihydrobis(4-cyano-3-tert-butylpyrazolylborate) ligand has been synthesized. Isolated crystals of the thallium complex were collected and structurally characterized by X-ray diffraction. Transition metal complexes of the ligand are currently under investigation.

This thesis presents ultrafast photophysical measurements on a number of phosphorescent iridium complexes and establishes relationships between the relaxation rates and the vibrational properties of the material. When ultrafast luminescence is measured on the peak of the phosphorescence spectrum and on its red-side, 230 fs and 3 ps decay time constants were observed in all materials studied, and this was attributed to population redistribution amongst the three electronic substates of the lowest triplet metal-ligand charge transfer (MLCT) state. The observation of luminescence at higher values of energy embodied ultrafast dissipation of excess energy by intramolecular vibrational redistribution (IVR) and it was found that the dissipation channels and rate of IVR could be modified by chemical modification of the emitting molecule. This was tested in two ways. Firstly by adding electronically inactive dendrons to the core, an increase in the preference for dissipation of excess energy by IVR rather than by picosecond cooling to the solvent molecules was found, but this did not change the rate of IVR. The second method of testing was by fusing a phenyl moiety directly onto the ligand, this both increased the rate of IVR and also the preference for dissipation by it rather than by picosecond cooling. Fluorescence was recorded in an iridium complex for the first time and a decay time constant of 65 fs was found, thus allowing a direct observation of intersystem crossing (ISC) to be made. In a deep red emitting iridium complex internal conversion (IC) and ISC were observed and the factors controlling their time constants deduced. IC was found to occur by dissipation of excess energy by IVR. The rate of IC was found to be dependent on the amount of vibrational energy stored in the molecule, with IC fast (< 45 fs) when < 0.6 eV of energy is stored and slower (~ 70 fs) when the value is > 0.6 eV. The rate of ISC agreed with these findings, indicating that the very process of ISC may be thought of as closely analogous to that of IC given the strongly spin-mixed nature of the singlet and triplet MLCT states.

Chemische Synthese und Charakterisierung von Sauerstoff- und Schwefel-Heteroporphyrinen und ihren Mn(II)-, Co(II)-, Cu(II)-, Zn(II)- und Pd(II)-Komplexen. Strukturelle und spektroskopische Beschreibung der Liganden und Komplexe durch Röntgendiffraktometrie, EXAFS, NMR, UVVIS, Fluoreszenzspektroskopie, CV unf MS. Darstellung und Beschreibung dendritischer Heteroporphyrinmoleküle.

No description available.

Chemische Synthese und Charakterisierung von Sauerstoff- und Schwefel-Heteroporphyrinen und ihren Mn(II)-, Co(II)-, Cu(II)-, Zn(II)- und Pd(II)-Komplexen. Strukturelle und spektroskopische Beschreibung der Liganden und Komplexe durch Röntgendiffraktometrie, EXAFS, NMR, UVVIS, Fluoreszenzspektroskopie, CV unf MS. Darstellung und Beschreibung dendritischer Heteroporphyrinmoleküle.

This thesis expands the scope for using the permethylpentalene ligand and its precursors in the synthesis of organometallic complexes. <strong>Chapter one</strong> begins with a brief review of linked metallocenes, with which multimetallic compounds bridged by pentalene ligands have often been compared, followed by a comprehensive review of the routes used to make pentalenes and substituted pentalenes. Organometallic compounds of pentalenes are introduced, with a focus on bimetallic systems. <strong>Chapter two</strong> explores the diversification of substituents added to the permethylpentalene (Pn*) precursor WeissH₄, to include ethyl and isopropyl groups. Low-symmetry mono-, di-, tri- and tetraalkylated products are formed, eight such organic molecules have been identified by NMR spectroscopy, and two characterised crystallographically. It has been demonstrated that subsequent hydrolysis and decarboxylation of two of these products produces low-symmetry alkylpentalene precursors. The chapter concludes with discussions on the selectivity exhibited in these reactions, and the assignment of stereochemistry. <strong>Chapter three</strong> describes the synthesis of the first homoleptic double metallocene complex of iron. Fe₂Pn*₂ has been characterised by X ray diffraction, and cyclic voltammetry studies demonstrate four accessible oxidation states (-1, 0, +1, +2). Magnetic measurements in the solid and solution state reveal an unusual triplet configuration, and DFT calculations indicate the origin of a high magnetic moment likely resides in unquenched orbital angular momentum contributions from SOMOs which have metal d character. Fe₂Pn*₂ is EPR silent at 5, 40, and 300 K both in solution and the solid state, suggesting a large zero-field splitting parameter. The reaction of the di-iron complex with carbon monoxide, ethylene and H2 is reported; the bimetallic CO adduct, Fe₂(&mu; &eta;⁵,&eta;³ Pn*)(&mu; &eta;⁵,&eta;¹ Pn*)(CO)₂, has been crystallographically characterised, and contains a highly distorted allylic bonding motif, which to the author’s knowledge is believed to be unique among iron complexes. <strong>Chapter four</strong> discusses the interaction of the bidentate Pn* ligand in anti bimetallic fused metallocenes. A new ligand exchange route has been developed to access the complexes (MCp)₂Pn* (M = Co, Ni), and the isostructural complexes (MCp*)₂Pn* have been made for M = Fe, Co, Ni by salt metathesis reactions. All five complexes have been characterised by single crystal X-ray crystallography, and have diamagnetic ground states in solution in common with their Pn bridged analogues. Variable temperature NMR studies reveal a spin-equilibrium between S = 0 and S = 1 in the dinickel complexes. DFT calculations reproduce the spin states found, and suggest the distortion towards &eta;³ coordination observed on crossing from Fe, to Co, to Ni, results from population of orbitals with M―bridgehead antibonding character. The electronic structures show it is important to draw comparisons between isoelectronic linked metallocenes. Electrochemical studies on the diiron, dicobalt, and (NiCp)₂Pn* complexes reveal at least three redox events for each. <strong>Chapter five</strong> documents the successful synthesis and characterisation of monometallic complexes of iron and manganese with Pn*H ligands. The isostructural complexes Fe(Pn*H)₂ and Mn(Pn*H)₂ can have been characterised crystallographically, and are potential precursors for accessing heterometallic, and multimetallic complexes. Mn(Pn*H)₂ is a rare example of a manganese sandwich compound and magnetic studies on a single isomer in the solution and solid states suggest it adopts intermediate spin states of S = 2 in solution, and S = 3/2 in the solid state. <strong>Chapter six</strong> gives experimental details for all syntheses and studies described in the preceding chapters. <strong>Chapter seven</strong> provides characterising data for all new compounds. Fitting data for VT NMR and SQUID studies are provided in the <strong>appendix</strong> at the end of this thesis. Crystallographic data in the form of .cif files, DFT output files, and raw SQUID data, can be found in the <strong>electronic appendix</strong>.

Neste trabalho foram projetados, fabricados e caracterizados funcionalmente dispositivos eletroluminescentes empregando complexos de Terras Raras (TR) e de Metais de Transição (MT) tanto como em filmes finos termicamente evaporados quanto formados através da técnica de spin-coating. O estudo foi iniciado com os complexos de TRs (especificamente o complexo de Európio e de Térbio) com filmes termicamente evaporados, com vistas à análise da eficiência externa dos dispositivos em função do ligante principal (CL). Desta análise observou-se que a particular estrutura química do CL resulta em diferenças perceptíveis ao nível da caracterização eletro-óptica (de 0,73x10-3 [BTA] para 1,05x10-3 [DBM]). Dando seqüência à análise de dispositivo com camada emissiva termicamente evaporada, foi realizada a análise do complexo de Térbio com dois tipos de ligante neutro (NL). Com base nos resultados obtidos, neste foco do estudo, observou-se que a configuração estrutural do NL implica em diferenças na eficiência externa (de 0,8x10-3 [PHEN] para 4,1x10- 3 [BIPY]) e no comprimento de onda dominante emitido (de 542 nm [BIPY] para 563 [PHEN]). Ainda explorando os complexos de TRs, foram estudados dispositivos empregando estes dispersos em um polímero com função de matriz, neste caso o polivinilcarbazol (PVK), em filmes formados por spin-coating, os quais apresentaram maior eficiência (de 0,72x10-3 [evaporado] para 1,24x10-3 [spincoating]) externa em comparação aos termicamente evaporados. Ainda nesta linha de estudo foi explorada uma nova estrutura de dispositivo empregando filmes automontados, cujos resultados apresentaram uma melhor eficiência externa para três bicamadas de PAni/PEDOT:PSS. Na seqüência, foram empregados os complexos de MT, especificamente de Rutênio e de Rênio, em filmes finos formados por spincoating. Com o primeiro destes, foi avaliada a conseqüência da variação do seu ligante, seus processos de transporte de portadores de carga e os fenômenos relacionados com sua luminescência. Já com o segundo, que foi disperso em PVK em diversas concentrações, foi feita a análise da eficiência externa com a mesma idéia adotada com o complexo de Európio, cujo estudo revelou uma eficiente transferência de energia, descrita pelo mecanismo de Transferência de Carga Metal- Ligante (3MLCT). / This work presents the study of the Rare Earth (RE) and Transition Metals (TM) complexes, as emissive layers of Organic Light-Emitting Devices (OLEDs) designed, built and electro-optically characterized. The thin films were thermally evaporated or spin-coated. This research started with the study of Europium complex changing its central ligand (CL), which showed that its electrical response exhibits external efficiency differences (from 0.73x10-3 [BTA] to 1.05x10-3 [DBM]). It was observed that the particular chemical structure of the CL results in significant differences as seen in the electro-optical characterization. Giving continuity to the thermally evaporated device characterization, an analysis was done with the Terbium complexes with two different neutral ligands (NL). It was noticed, in this work, that an NL change in Terbium complex imply in changes in external efficiency (from 0.8x10-3 [PHEN] to 4.1x10-3 [BIPY]) and in the emitted dominant wavelength (from 542 nm [BIPY] to 563 nm [PHEN]). Following the study using RE complex, we used it as a dye dispersed in polyvinylcarbazole (PVK) matrix, in a spin-coated deposited thin-film, which results showed a better external efficiency in comparison with thermally evaporated thin-films (from 0.72x10-3 [thermal evaporation] to 1.24x10-3 [spin-coating]). Besides, it was studied a new structure of electroluminescent device with thin-film Self-Assembled deposition, which results showed a better external efficiency for three bilayers of PAni/PEDOT:PSS. In the sequence, TM complexes, namely Ruthenium and Rhenium, were studied using spincoated thin-films. With the first of them, the implications of different ligands (bipyridyne and phenanthroline) were evaluated aiming the charge carrier transport and the luminescence related phenomena. The Rhenium complex was dispersed as a dye in the PVK, using the same approach as that used to study the Europium complex showing a very efficient energy transfer process, described in literature as the Metal-Ligand Charge Transfer (3MLCT) mechanism.