Metalosupramoléculas discretas e Metal Organic Frameworks (MOFs) baseados em íons lantanídeos: design, síntese, caracterização e propriedades

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Propriedades luminescentes de polioxometalato contendo európio(III) correlacionadas à sua conformação em sólido estendido e em filmes auto-organizados de Langmuir e Langmuir-Blodgett

Pós-graduação em Química - IQ

Molecular Dynamics Investigations of PRODAN in a DLPC Bilayer

Molecular dynamics computer simulations have been performed to identify preferred positions of the fluorescent probe PRODAN in a fully hydrated DLPC bilayer in the fluid phase. In addition to the intramolecular charge-transfer first vertical excited state, we considered different charge distributions for the electronic ground state of the PRODAN molecule by distinct atomic charge models corresponding to the probe molecule in vacuum as well as polarized in a weak and a strong dielectric solvent (cyclohexane and water). Independent on the charge distribution model of PRODAN, we observed a preferential orientation of this molecule in the bilayer with the dimethylamino group pointing toward the membrane's center and the carbonyl oxygen toward the membrane's interface. However, changing the charge distribution model of PRODAN, independent of its initial position in the equilibrated DLPC membrane, we observed different preferential positions. For the ground state representation without polarization and the in-cyclohexane polarization, the probe maintains its position close to the membrane's center. Considering the in-water polarization model, the probe approaches more of the polar headgroup region of the bilayer, with a strong structural correlation with the choline group, exposing its oxygen atom to water molecules. PRODAN's representation of the first vertical excited state with the in-water polarization also approaches the polar region of the membrane with the oxygen atom exposed to the bilayer's hydration shell. However, this model presents a stronger structural correlation with the phosphate groups than the ground state. Therefore, we conclude that the orientation of the PRODAN molecule inside the DLPC membrane is well-defined, but its position is very sensitive to the effect of the medium polarization included here by different models for the atomic charge distribution of the probe.

Copper(I) phenanthroline complexes and supramolecular systems containing fullerenes: Photophysics, photochemistry and potential applications in sustainable energy technologies.

Chemistry can contribute, in many different ways to solve the challenges we are facing to modify our inefficient and fossil-fuel based energy system. The present work was motivated by the search for efficient photoactive materials to be employed in the context of the energy problem: materials to be utilized in energy efficient devices and in the production of renewable electricity and fuels. We presented a new class of copper complexes, that could find application in lighting techhnologies, by serving as luminescent materials in LEC, OLED, WOLED devices. These technologies may provide substantial energy savings in the lighting sector. Moreover, recently, copper complexes have been used as light harvesting compounds in dye sensitized photoelectrochemical solar cells, which offer a viable alternative to silicon-based photovoltaic technologies. We presented also a few supramolecular systems containing fullerene, e.g. dendrimers, dyads and triads.The most complex among these arrays, which contain porphyrin moieties, are presented in the final chapter. They undergo photoinduced energy- and electron transfer processes also with long-lived charge separated states, i.e. the fundamental processes to power artificial photosynthetic systems.

Morphology and charge transport in conjugated polymers

To assist rational compound design of organic semiconductors, two problems need to be addressed. First, the material morphology has to be known at an atomistic level. Second, with the morphology at hand, an appropriate charge transport model needs to be developed in order to link charge carrier mobility to structure.rnrnThe former can be addressed by generating atomistic morphologies using molecular dynamics simulations. However, the accessible range of time- and length-scales is limited. To overcome these limitations, systematic coarse-graining methods can be used. In the first part of the thesis, the Versatile Object-oriented Toolkit for Coarse-graining Applications is introduced, which provides a platform for the implementation of coarse-graining methods. Tools to perform Boltzmann inversion, iterative Boltzmann inversion, inverse Monte Carlo, and force-matching are available and have been tested on a set of model systems (water, methanol, propane and a single hexane chain). Advantages and problems of each specific method are discussed.rnrnIn partially disordered systems, the second issue is closely connected to constructing appropriate diabatic states between which charge transfer occurs. In the second part of the thesis, the description initially used for small conjugated molecules is extended to conjugated polymers. Here, charge transport is modeled by introducing conjugated segments on which charge carriers are localized. Inter-chain transport is then treated within a high temperature non-adiabatic Marcus theory while an adiabatic rate expression is used for intra-chain transport. The charge dynamics is simulated using the kinetic Monte Carlo method.rnrnThe entire framework is finally employed to establish a relation between the morphology and the charge mobility of the neutral and doped states of polypyrrole, a conjugated polymer. It is shown that for short oligomers, charge carrier mobility is insensitive to the orientational molecular ordering and is determined by the threshold transfer integral which connects percolating clusters of molecules that form interconnected networks. The value of this transfer integral can be related to the radial distribution function. Hence, charge mobility is mainly determined by the local molecular packing and is independent of the global morphology, at least in such a non-crystalline state of a polymer.

Donor–acceptor systems in the quest for organic semiconductors

Die letzten Jahrzehnte brachten eine Vielzahl neuer organischen Halbleiter hervor, welche erfolgreich als aktive Materialien in Bauteilen eingesetzt wurden, wie zum Beispiel Feldeffekttransistoren (FET), organische Leuchtdioden (OLED), organischen Photovoltaikzellen (OPV) und Sensoren. Einige dieser Materialien haben, obwohl sich die Technolgie noch in der „Pubertät“ befindet, die minimalen Anforderungen für eine kommerzielle Anwendung erreicht, wobei jedoch vieles noch zu entdecken, erklären und verstehen bleibt. Diese Arbeit beschreibt das Design, die Synthese und Charakterisierung neuartiger halbleitender Polymere mit speziell eingestellten optoelektronischen Eigenschaften, welche effiziente ambipolare oder n-Leitung in OFET’s und OPV’s zeigen. Das Hauptziel wurde dadurch erreicht, dass sowohl die vorteilhaften Eigenschaften des planaren, elektronenarmen heterozyklischen Bausteines Thiadiazolo[3,4-g]quinoxalin als auch von Ethinbrücken, welche den Donor (D) und den Akzeptor (A) in einem D-A-Copolymer verbinden, durch systematische Optimierung ausgenutzt wurden. Neben synthetischen Herausforderungen werden in dieser Arbeit auch detailiiete Untersuchungen der optoelektronischen Eigenschaften der hergestellten konjugierten Polymere und Modellverbindungen dargelegt. Darüber hinaus beschreibt diese Arbeit erstmals ein Beispiel für ein Polymer, welches Dreifachbindungen im Polymerrückgrat enthält, und nahezu eine ausgeglichene ambipolare Ladungsträgerleitung in OFET’s zeigt. Zusätzlich werden gemischt-valente Phenothiazine, verbrückt mittels elektronenarmen pi-Brücken wie etwa Benzo[c][2,1,3]thiadiazol, und deren Elektronentransferprozesse, im Rahmen der Marcus-Hush-Theorie, untersucht.

Charge-transport simulations in organic semiconductors

In this thesis we have extended the methods for microscopic charge-transport simulations for organic semiconductors. In these materials the weak intermolecular interactions lead to spatially localized charge carriers, and the charge transport occurs as an activated hopping process between diabatic states. In addition to weak electronic couplings between these states, different electrostatic environments in the organic material lead to a broadening of the density of states for the charge energies which limits carrier mobilities.rnThe contributions to the method development includern(i) the derivation of a bimolecular charge-transfer rate,rn(ii) the efficient evaluation of intermolecular (outer-sphere) reorganization energies,rn(iii) the investigation of effects of conformational disorder on intramolecular reorganization energies or internal site energiesrnand (iv) the inclusion of self-consistent polarization interactions for calculation of charge energies.These methods were applied to study charge transport in amorphous phases of small molecules used in the emission layer of organic light emitting diodes (OLED).rnWhen bulky substituents are attached to an aromatic core in order to adjust energy levels or prevent crystallization, a small amount of delocalization of the frontier orbital to the substituents can increase electronic couplings between neighboring molecules. This leads to improved charge-transfer rates and, hence, larger charge-mobility. We therefore suggest using the mesomeric effect (as opposed to the inductive effect) when attaching substituents to aromatic cores, which is necessary for example in deep blue OLEDs, where the energy levels of a host molecule have to be adjusted to those of the emitter.rnFurthermore, the energy landscape for charges in an amorphous phase cannot be predicted by mesoscopic models because they approximate the realistic morphology by a lattice and represent molecular charge distributions in a multipole expansion. The microscopic approach shows that a polarization-induced stabilization of a molecule in its charged and neutral states can lead to large shifts, broadening, and traps in the distribution of charge energies. These results are especially important for multi-component systems (the emission layer of an OLED or the donor-acceptor interface of an organic solar cell), if the change in polarizability upon charging (or excitation in case of energy transport) is different for the components. Thus, the polarizability change upon charging or excitation should be added to the set of molecular parameters essential for understanding charge and energy transport in organic semiconductors.rnWe also studied charge transport in self-assembled systems, where intermolecular packing motives induced by side chains can increase electronic couplings between molecules. This leads to larger charge mobility, which is essential to improve devices such as organic field effect transistors, where low carrier mobilities limit the switching frequency.rnHowever, it is not sufficient to match the average local molecular order induced by the sidernchains (such as the pitch angle between consecutive molecules in a discotic mesophase) with maxima of the electronic couplings.rnIt is also important to make the corresponding distributions as narrow as possible compared to the window determined by the closest minima of thernelectronic couplings. This is especially important in one-dimensional systems, where charge transport is limited by the smallest electronic couplings.rnThe immediate implication for compound design is that the side chains should assist the self-assemblingrnprocess not only via soft entropic interactions, but also via stronger specific interactions, such as hydrogen bonding.rnrnrnrn

Interfacial interactions, charge transport and growth phenomena in Organic Field Effect Transistors

Organic electronics is an emerging field with a vast number of applications having high potential for commercial success. Although an enormous progress has been made in this research area, many organic electronic applications such as organic opto-electronic devices, organic field effect transistors and organic bioelectronic devices still require further optimization to fulfill the requirements for successful commercialization. The main bottle neck that hinders large scale production of these devices is their performances and stability. The performance of the organic devices largely depends on the charge transport processes occurring at the interfaces of various material that it is composed of. As a result, the key ingredient needed for a successful improvement in the performance and stability of organic electronic devices is an in-depth knowledge of the interfacial interactions and the charge transport phenomena taking place at different interfaces. The aim of this thesis is to address the role of the various interfaces between different material in determining the charge transport properties of organic devices. In this framework, I chose an Organic Field Effect Transistor (OFET) as a model system to carry out this study as it An OFET offers various interfaces that can be investigated as it is made up of stacked layers of various material. In order to probe the intrinsic properties that governs the charge transport, we have to be able to carry out thorough investigation of the interactions taking place down at the accumulation layer thickness. However, since organic materials are highly instable in ambient conditions, it becomes quite impossible to investigate the intrinsic properties of the material without the influence of extrinsic factors like air, moisture and light. For this reason, I have employed a technique called the in situ real-time electrical characterization technique which enables electrical characterization of the OFET during the growth of the semiconductor.

Exploratory studies on coordination chemistry of a redox-active bridging ligand: synthesis, properties and solid state structures of the complexes

The explorative coordination chemistry of the bridging ligand TTF-PPB is presented. Its strong binding ability to Co(II) and then to Ni(II) or Cu(II) in the presence of hexafluoroacetylacetonate (hfac(-)), forming new mono-and dinuclear complexes 1-3, is described. X-ray crystallographic studies have been conducted in the case of the free ligand TTF-PPB as well as its complexes [Co(TTF-PPB)(hfac)(2)] (1) and [Co(hfac)(2)(mu-TTF-PPB)Ni(hfac)(2)] (2). Each metal ion is bonded to two bidentate hfac-anions through their oxygen atoms and two nitrogen atoms of the PPB moiety with a distorted octahedral coordination geometry. Specifically, nitrogen donor atoms of TTF-PPB adopt a cis-coordination but not in the equatorial plane, which is quite rare. Electronic absorption, photoinduced intraligand charge transfer ((1)ILCT), and electrochemical behaviour of 1-3 have been investigated. UV-Vis spectroscopy shows very strong bands in the UV region consistent with ligand centred pi-pi* transitions and an intense broad band in the visible region corresponding to a spin-allowed pi-pi* (1)ILCT transition. Upon coordination, the (1)ILCT band is bathochromically shifted by 3100, 6100 and 5900 cm(-1) on going from 1 to 3. The electrochemical studies reveal that all of them undergo two reversible oxidation and one reversible reduction processes, ascribed to the successive oxidations of the TTF moiety and the reduction of the PPB unit, respectively.

Effect of the Addition of a Fused Donor-Acceptor Ligand on a Ru(II) Complex: Synthesis, Characterization, and Photoinduced Electron Transfer Reactions of Ru(TTF-dppz)(2)(Aqphen) (2+)

The synthesis and the photophysical properties of the complex [Ru(TTF-dppz)(2)(Aqphen)](2+) (TTF = tetrathiafulvalene, dppz = dipyrido-[3,2-a:2',3'-c]phenazine, Aqphen = anthraquinone fused to phenanthroline via a pyrazine bridge) are described. In this molecular triad excitation into the metal ligand charge transfer bands results in the creation of a long-lived charge separated state with TTF acting as electron donor and anthraquinone as terminal acceptor. The lifetime of the charge-separated state is 400 ns in dichloromethane at room temperature. A mechanism for the charge separation involving an intermediate charge-separated state is proposed based on transient absorption spectroscopy.

A Pt(II) complex with both a phenanthroline and a tetrathiafulvalene-extended dithiolate ligand: Synthesis, crystal structure, electrochemical and spectroscopic properties

The reaction of 4,5-bis(2'-cyanoethylsulfanyl)-4',5'-dipropylthiotetrathiafulvalene with Pt(phen)Cl-2 (phen = 1,10-phenanthroline) with CsOH as base in CH3OH-THE affords the target complex I in 44% yield. This complex crystallizes in the monoclinic space group P2(1)/c, M = 790.01, a = 12.1732(12), b = 15.851(2), c = 14.5371(16) angstrom, beta = 107.693(12)degrees, V = 2672.4(5) angstrom(3) and Z = 4. It undergoes two reversible single-electron oxidation and two irreversible reduction processes. An intense electronic absorption band at 15200 cm(-1) (658 nm) in CH2Cl2 is assigned to the intramolecular mixed metal/ligand-to-ligand charge transfer (LLCT) from a tetrathiafulvalene-extended dithiolate-based HOMO to a phenanthroline-based LUMO. This band shifts hypsochromically with increasing solvent polarity. Systematic changes in the optical spectra upon oxidation allow precise tuning of the oxidation states of 1 and reversible control over its optical properties. Irradiation of 1 at 15625 cm(-1) (640 nm) in glassy solution below 150K results in emission from the (LLCT)-L-3 excited state. GRAPHICS (C) 2013 Elsevier Ltd. All rights reserved.

Simulating Energy Transfer and Upconversion in β-NaYF 4 : Yb 3+ , Tm 3+

The design of upconversion phosphors with higher quantum yield requires a deeper understanding of the detailed energy transfer and upconversion processes between active ions inside the material. Rate equations can model those processes by describing the populations of the energy levels of the ions as a function of time. However, this model presents some drawbacks: energy migration is assumed to be infinitely fast, it does not determine the detailed interaction mechanism (multipolar or exchange), and it only provides the macroscopic averaged parameters of interaction. Hence, a rate equation model with the same parameters cannot correctly predict the time evolution of upconverted emission and power dependence under a wide range of concentrations of active ions. We present a model that combines information about the host material lattice, the concentration of active ions, and a microscopic rate equation system. The extent of energy migration is correctly taken into account because the energy transfer processes are described on the level of the individual ions. This model predicts the decay curves, concentration, and excitation power dependences of the emission. This detailed information can be used to predict the optimal concentration that results in the maximum upconverted emission.

Long-time quantum simulation of the primary charge separation in bacterial photosynthesis.

Accurate quantum mechanical simulations of the primary charge transfer in photosynthetic reaction centers are reported. The process is modeled by three coupled electronic states corresponding to the photoexcited chlorophyll special pair (donor), the reduced bacteriopheophytin (acceptor), and the reduced accessory chlorophyll (bridge) that interact with a dissipative medium of protein and solvent degrees of freedom. The time evolution of the excited special pair is followed over 17 ps by using a fully quantum mechanical path integral scheme. We find that a free energy of the reduced accessory chlorophyll state approximately equal to 400 cm(-1) lower than that of the excited special pair state yields state populations in agreement with experimental results on wild-type and modified reaction centers. For this energetic configuration electron transfer is a two-step process.

Potentiation of proton transfer function by electrostatic interactions in photosynthetic reaction centers from Rhodobacter sphaeroides: First results from site-directed mutation of the H subunit.

The x-ray crystallographic structure of the photosynthetic reaction center (RC) has proven critical in understanding biological electron transfer processes. By contrast, understanding of intraprotein proton transfer is easily lost in the immense richness of the details. In the RC of Rhodobacter (Rb.) sphaeroides, the secondary quinone (QB) is surrounded by amino acid residues of the L subunit and some buried water molecules, with M- and H-subunit residues also close by. The effects of site-directed mutagenesis upon RC turnover and quinone function have implicated several L-subunit residues in proton delivery to QB, although some species differences exist. In wild-type Rb. sphaeroides, Glu L212 and Asp L213 represent an inner shell of residues of particular importance in proton transfer to QB. Asp L213 is crucial for delivery of the first proton, coupled to transfer of the second electron, while Glu L212, possibly together with Asp L213, is necessary for delivery of the second proton, after the second electron transfer. We report here the first study, by site-directed mutagenesis, of the role of the H subunit in QB function. Glu H173, one of a cluster of strongly interacting residues near QB, including Asp L213, was altered to Gln. In isolated mutant RCs, the kinetics of the first electron transfer, leading to formation of the semiquinone, QB-, and the proton-linked second electron transfer, leading to the formation of fully reduced quinol, were both greatly retarded, as observed previously in the Asp L213 --> Asn mutant. However, the first electron transfer equilibrium, QA-QB <==> QAQB-, was decreased, which is opposite to the effect of the Asp L213 --> Asn mutation. These major disruptions of events coupled to proton delivery to QB were largely reversed by the addition of azide (N3-). The results support a major role for electrostatic interactions between charged groups in determining the protonation state of certain entities, thereby controlling the rate of the second electron transfer. It is suggested that the essential electrostatic effect may be to "potentiate" proton transfer activity by raising the pK of functional entities that actually transfer protons in a coupled fashion with the second electron transfer. Candidates include buried water (H3O+) and Ser L223 (serine-OH2+), which is very close to the O5 carbonyl of the quinone.

Thermal decomposition of the different particles size fractions of almond shells and olive stones. Thermal behaviour changes due to the milling processes

The aim of this study is to investigate the effect of particle size on the non-isothermal pyrolysis of almond shells (AS) and olive stones (OS) and to show possible differences in the composition of the different fractions obtained after milling and sieving. The results obtained from the study of different particle size of AS and OS samples show significant differences in the solid residue obtained and in the shape and overlapping degree of the peaks, especially with the smaller particle size. These differences can be due to different factors: (a) the amount of inorganic matter, which increases as particle size decreases, (b) heat and mass transfer processes, (c) different sample composition as a consequence of the milling process which may provoke changes in the structure and the segregation of the components (in addition to the ashes) increasingly changes the composition of the sample as the particle size decreases.