No description available.

The assembly of nanostructures into “multi”-dimensional materials is one of the main topics occurring in nanoscience today. It is now possible to produce high quality nanostructures reproducibly but for their further application larger structures that are easier to handle are required. Nevertheless during their assembly their nanometer size and accompanying properties must be maintained. This challenge was addressed in this work. Lead chalcogenides have been chosen as an example system because they are expected to offer great opportunities as thermoelectric materials. Three different ways to achieve assemblies of lead chalcogenide nanostructures were used and the resulting structures characterized with respect to their potential application as thermoelectric material. The first means by which a “multi”-dimensional assembly of lead chalcogenide quantum dots can be produced is the formation of porous structures such as aerogels and xerogels. A procedure, where the addition of an initiator such as oxidizers or incident radiation is unnecessary, is introduced and the formation process studied by absorption spectroscopy. The time-consuming aggregation step could be significantly reduced by employing a slightly elevated temperature during gelation that does not lead to any observable differences within the resulting gel structures. After either supercritical or subcritical drying, highly porous monolithic gel structures can be achieved. During the gel formation the size and the shape of the particles changed and they were directly linked together. Nevertheless the resulting porous structures remain crystalline and size dependent effects of the optical properties could be shown. Gels produced from a mixture of PbS and PbSe QDs show a homogenous distribution of both materials but it is not clear to what extent they form an alloy. Although the particles are directly linked together the resulting porous structures possess a very high resistivity and so it was not possible to characterize the semiconductor aerogels with regard to their thermoelectric properties. To achieve an enhanced conductivity porous structures containing PbS and Au nanoparticles have been produced. As has been seen for the pure semiconductor gels the size of the PbS quantum dots has increased and elongated particles were formed. In contrast to the PbS QDs the Au nanoparticles did not change their size and shape and are unevenly distributed within the PbS network. Through the use of the gold nanoparticles the conductivity could be increased and although the conductivity is still quite small, it was possible to determine Seebeck coefficients near room temperature for a mixed semiconductor-metal gel. The second means by which QD solids could be formed was by the compaction of the QD building blocks into a material that is still nanostructured. Therefore the synthesis of PbS was optimized to achieve sufficient amounts of PbS quantum dots. The ligands used in the synthesis of the QDs unfortunately act as an insulating layer resulting in QD solids with resistivities as high as 2 Gigaohm. For this reason different surface modification strategies were introduced to minimize the interparticle distance and to increase the coupling between the QDs so as to increase the conductivity of the resulting quantum dot solids. One very promising method was the exchange of the initial ligands by shorter ones that can be destroyed at lower temperatures. By such heat treatments the resistivity could be decreased by up to six orders of magnitude. For the pressing of the quantum dots two different compaction methods (SPS and hydraulic pressing) were compared. While the grain growth within the SPS pressed samples is significantly higher the same densification can be achieved by a cold hydraulic pressing as well as by SPS. The densification could be further increased through the use of preheated PbS QDs due to the destruction of the ligands. Samples which had been surface modified with MPA and subsequently thermally treated show the best results with respect to their thermopower and resistivities. Nevertheless the conductivity of the QD solids is still too high for them to be used as efficient thermoelectric materials. The final assembly method does not involve QDs but instead with one dimensional nanowires. Therefore a synthesis was developed that enables the formation of PbS nanowires of different diameters and one that is easy up-scalable. By the use of a less reactive sulfur precursor and an additional surfactant the formation of nuclei is significantly retarded and within an annealing time of two hours nanowires can be formed presumably by an oriented attachment mechanism. Single crystalline nanowires with a diameter of 65-105 nm could be achieved with the longest axes of the nanowires being parallel to [100]. The resulting nanowires were used as building blocks for film formation on glass substrates by an easily implemented method that requires no special equipment. To characterize the films with a view to their possible application as a thermoelectric material, surface modifications of the films were performed to improve the charge transfer in the films and the Seebeck coefficients of the resulting films measured. Therefore the previous approach of using MPA was applied and a subsequent thermal treatment demonstrated very promising results. In addition an crosslinking ligand was used for surface treatment that leads to similar results as was observed for the thermally treated MPA approach. Both approaches lead to an order of magnitude decrease in the resistivity and due to the fewer grain boundaries present in the films composed of nanowires as compared to the QD assemblies the conductivity is significantly higher. The Seebeck coefficient measurements show that the thermal treatment only slightly affects the Seebeck coefficients. Therefore a significantly higher power factor could be achieved for the nanowire films than for the QD solids.

We present the bioconjugation of avidin as a central and/or bridging building block with mono-, bi- and tetravalent biotinylated glycodendrimers to fabricate defined supramolecular nanostructures for future (bio)medical applications. For this purpose mono-, bi- and tetravalent biotinylated glycodendrimers, decorated with short alkyl-linked or long PEG-linked biotin ligands, were synthesized and characterized by NMR, IR and mass spectrometry and HABA displacement assay. Various techniques (UV/Vis, DLS, TEM, LILBID-MS and AF4) were used in order to obtain information about the structural properties of different conjugates of avidin and mono-, bi- and tetravalent biotinylated glycodendrimers. The biotin ligand’s spacer length, its chemical structure and the degree of biotin functionalization are essential parameters in the formation of nanostructures with avidin having a controlled composition and size dimension up to 100 nm. Biohybrid structures with avidin as a central unit require monovalent glycodendrimers with PEG-linked biotin, while bi- and tetravalent glycodendrimers with short alkyl-linked biotin ligands are more efficient than their counterparts with longer PEG–biotin ligands in the fabrication of defined biohybrid structures (∅ up to 100 nm) with avidin as a bridging unit. The most dominating key issue, combined with other conjugation issues, is the optimal ligand–receptor stoichiometry to fabricate biohybrid structures with diameter of <20, <30 or up to 100 nm.

We report on an efficient assembly approach to a variety of electrostatically stabilized all-inorganic semiconductor nanocrystals (NCs) via their linking with appropriate ions into multibranched gel networks. These all-inorganic non-ordered 3D assemblies can combine strong interparticle coupling which facilitates charge transport between the NCs with their diverse morphology, composition, size, and functional capping ligands. Moreover, the resulting dry gels (aerogels) are highly porous monolithic structures, which preserve the quantum confinement of their building blocks. The inorganic semiconductor aerogel made of 4.5 nm CdSe colloidal NCs, capped with iodide ions and bridged with Cd2+ ions, exhibited a surface area as high as 146 m2/g.

This dissertation presents the investigation of magnetic exchange and anisotropy in novel metal-organic complexes containing minimum number of magnetic ions. Such complexes can serve as a model system to understand the exciting magnetic phenomena in such class of materials and also can put forward as candidates for the so called molecular nanomagnets. A direct assessment of the effective magnetic moment and the effective interaction between the metal ions in the complex can be done using magnetization measurements. Here the magnetization studies are performed as a function of temperature and field using a SQUID magnetometer. Yet another powerful tool to characterize and determine the spin levels, the ESR spectroscopic methods, has also been exploited. The study of the dynamical properties of this class of materials was relevant to understand the relaxation mechanism in the low temperatures. For this a new ac susceptometer has been built in house which was another main objective of this dissertation work. The design, fabrication, calibration and automation done on this device is presented in this thesis. The device has been tested using the known molecular magnet Mn12 acetate, and the antiferromagnet Dy2PdSi3. The present work is mainly focused on the magnetic properties of Mn, Ni and Fe based organometallic complexes. The studied Mn dimer with different acceptor and donor ligands exhibit the fine tuning of the electron density at the core of molecular complex by variation in ligands. This in turn shows that the change in peripheral ligands can control the magnetism of the molecule. The influence of the change in Ni-S-Ni bond angle in the magnetic exchange interaction is studied in a Ni(2) dimer and a Ni(2) trimer complex. The Ni dimer complex shows a ferromagnetic interaction (J = -42K) whereas trimer shows an antiferromagnetic interaction (J = 140K). Another Ni based complex bridged via phosphorous has been studied which shows the existence of glassy nature at low temperature. Also a polymeric chain compound based on Fe is studied and presented. All these phosphorous or sulphur bridged complexes are novel materials and these are the first data on these complexes.

No description available.

A bifunctional imidazolium linker was used for the production of highly crosslinked element organic frameworks by Suzuki-coupling with tetrafunctional boronic acids. The resulting porous materials are good heterogeneous organocatalysts in the N-heterocyclic carbene-catalyzed conjugated umpolung of α,β-unsaturated cinnamaldehyde. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Aufgrund ihrer Eigenschaften und möglicher Anwendungen werden Siliciumkomplexe mit O,N,O´-Ligandsystemen in der Literatur beschrieben. Jedoch fehlen bisher Untersuchungen zur Strukturaufklärung. Im Rahmen dieser Arbeit wurden zahlreiche Silicium-, Germanium- und Zinnkomplexe mit chiralen O,N,O´-Liganden synthetisiert und strukturanalytisch charakterisiert. Dazu wurden die Liganden durch Kondensationsreaktionen von enantiomerenreinen Aminosäuren mit aromatischen ortho-Hydroxyaldehyden bzw. Acetylaceton hergestellt. Die weitere Umsetzung der Liganden mit Elementhalogeniden der Gruppe 14 führte zu den angestrebten Komplexverbindungen. Alle hergestellten Verbindungen wurden umfassend charakterisiert (NMR-, UV/Vis-, IR-Spektroskopie, Elementaranalyse, Einkristallstrukturanalyse, Drehwert). Quantenchemische Berechnungen an einfachen Modellverbindungen sowie an hergestellten Silicium- und Zinnkomplexen führten zu einem grundlegenden Verständnis der Festkörper-NMR-Parameter dieser Verbindungsklasse.

Oxygenierungs- und Oxidationsreaktionen sind in unserem Alltag allgegenwärtig und von großer Bedeutung. Sie finden Anwendung von der Natur bis hin zur Industrie. Der Einsatz von O2 als Sauerstoffquelle bzw. Oxidationsmittel ist besonders erstrebenswert. Die Erforschung der Aktivierung von O2 an Übergangsmetallkomplexen und Untersuchung der Reaktivität der resultierenden Verbindung ist von großer Bedeutung für das Verständnis dieser Reaktionen und Mechanismen. In dieser Arbeit wurde zunächst der Komplex trans-[Ir(4-C5F4N)(CNtBu)(PiPr3)2] synthetisiert, welcher mit dem 4-C5F4N- und dem CNtBu-Liganden stabilisierende Komponenten und wertvolle analytische Sonden enthält. Ausgehend von dieser Iridium(I)-Verbindung konnte auf verschiedenen Wegen der Peroxidokomplex trans-[Ir(4-C5F4N)(O2)(CNtBu)(PiPr3)2] erhalten und umfangreich charakterisiert werden. In Gegenwart von [Fe(C5H5)2][PF6] konnten Hinweise auf einen redoxkatalysierten Mechanismus gewonnen werden. Im nächsten Abschnitt konnte gezeigt werden, dass sich der Peroxidokomplex durch Bronstedsäuren aktivieren lässt. So wurde z.B. unter der Verwendung von Säuren wie HCl, CF3COOH oder HF die Bildung von H2O2 erzielt. Dabei entstehen die entsprechenden Iridium(III)-Komplexe mit den koordinierten Säureanionen. In Gegenwart von HCOOH werden ein Carbonatokomplex und H2 als Hauptprodukte gebildet und es konnten Hinweise zum Mechanismus dieser komplexen Reaktion gewonnen werden. Des Weiteren sind Lewissäuren und Elektrophile in der Lage, die metallgebundene Disauerstoffeinheit des Peroxidokomplexes zu aktivieren. Dazu wurden unter Anderem Silane und Borane eingesetzt. Im Fall von ClSiMe3 und BClCy2 konnten während der Reaktion Intermediate detektiert und analysiert werden. Tragen die Lewissäuren Chloratome wird die entsprechende Dichloridoiridium(III)-Verbindung gebildet. Durch Einsatz von BPh3 konnte eine veränderte Reaktivität erreicht werden und der Ausgangskomplex trans-[Ir(4-C5F4N)(CNtBu)(PiPr3)2] zurückerhalten werden. / Oxygenation- and oxidation reactions are ubiquitous and of great importance to our daily life. They find application from nature to industry. The use of O2 as an oxygen source or oxidation reagent, respectively, is particularly desirable. The research on the activation of O2 at transition metal complexes and the investigations of the reactivity of the resulting compounds is of great significance for the understanding of these reactions and mechanisms. Herein, this work describes the synthesis of the complex trans-[Ir(4-C5F4N)(CNtBu)(PiPr3)2], which incorporates stabilizing and valuable analytical elements provided by the 4-C5F4N and CNtBu ligands. Starting from this iridium(I) compound, the peroxido complex trans-[Ir(4-C5F4N)(O2)(CNtBu)(PiPr3)2] could be synthesized using different methods. In the presence of [Fe(C5H5)2][PF6], indications for a redox catalyzed mechanism could be provided. The next chapter shows that Bronsted acids are capable of activating the peroxido complex. With the help of acids like HCl, CF3COOH or HF, for example, the formation of H2O2 was achieved. Thereby, the corresponding iridium(III) complexes with the coordinating anions are formed. In the presence of HCOOH, a carbonato complex and H2 are formed as main products and ideas for the mechanism of this complex reaction were indicated. Furthermore, Lewis acids and electrophiles have the ability to activate the metal bound dioxygen moiety of the peroxido complex. Silanes and boranes were used for this purpose amongst others. In case of ClSiMe3 and BClCy2, intermediates of the reactions could be detected and analysed. If the Lewis acids carry chloride atoms, the corresponding dichlorido iridium(III) compounds were formed. BPh3 enabled a different reactivity and allowed the isolation of the starting material trans-[Ir(4C5F4N)(CNtBu)(PiPr3)2].

Im Rahmen dieser Arbeit wurden Siliciumkomplexe mit dianionischen Pyrrol-2-carbaldimin-funktionalisierten N,N,O- und N,N,N,N-Chelatliganden synthetisiert und kristallografisch, NMR- und UV/Vis-spektroskopisch und mittels quantenchemischer Berechnungen charakterisiert. Die pentakoordinierten Si-Komplexe mit N,N,O-Ligandrückgraten wiesen in Abhängigkeit von den weiteren Si-gebundenen Substituenten unterschiedlich konfigurierte verzerrt trigonal-bipyramidale Si-Koordinationssphären auf. Die Ursache der Farbigkeit dieser Verbindungen konnte mittels quantenchemischer Berechnungen detailliert erklärt werden. – Die Si-Komplexe mit N,N,N,N-Ligandrückgraten liegen in Abhängigkeit von den weiteren Si-gebundenen Substituenten als 5-fach koordinierte kationische oder neutrale 6-fach koordinierte Si-Komplexe vor. Deren Farbigkeit wurde mittels UV/VIS-Spektroskopie untersucht. Von ausgewählten Komplexen wurden die Tensoren der 29Si-NMR-Verschiebung rechnerisch und CP/MAS-NMR-spektroskopisch bestimmt.