New metallomolecular wires based on carbon-rich bridging systems: a systematic study

This dissertation presents and discusses the preparation of molecular wires (MW) candidates that would then be probed for electron transfer properties. These wires are bridged by 1,4-diethynylbenzene derivatives with alkoxy side chains with palladium and ruthenium metal complex termini. Characterization of these compounds was performed by usual spectroscopic techniques like 1H, 13C{1H} and 31P{1H} NMR, MS, FTIR and UV-Vis as well as by cyclic voltammetry which allowed classifying the candidates in the Robin–Day system and determination of bridges side chain and length effects on electronic transport. Preparation of the 1,4-diethynylbenzene derivatives was done with synthetic pathways that relied heavily in palladium catalyzed cross-couplings (Sonogashira). A family of single ringed 1,4-diethynylbenzene ligands with different length alkoxy side chains (OCH3, OC2H5, OC7H15) was thus prepared allowing for the influence of these ring decorations to be assessed. The ruthenium binuclear rods showed communication between metal centres only when the shorter ligands were used whereas the longer Ru complexes showed only one redox pair in CV studies which is in agreement to non-communicating metal centres. Cyclic voltammetry studies show irreversible one wave processes for palladium dinuclear complexes, making these rods function as molecular insulators. Fluorescence decay studies performed on the prepared compounds (ligands and complexes) show a pattern of decreasing decay times upon coordination to the metal centres which can due to ligand charge redistribution upon coordination leading to non-radiative relaxation paths. Regarding the X-ray structures, two new ligand related structures were obtained as well as new structure for a palladium rod. The effect of the side chains was observed to be important to the wires’ electronic properties when comparing with the analogues without a side chain. The effect brought by longer chains is nevertheless almost negligible.

A situation awareness interface for a bi-wheeled industrial hovercraft: design, development and evaluation

The intention of this thesis is to develop a prototype interface that enables an operator to control a bi-wheeled industrial hovercraft that will work within a fusion power plant if the automation system fails. This fusion power plant is part of the ITER project a conjoint effort of various industrialized countries to develop cleaner sources of energy. The development of the interface prototype will be based on situation awareness concepts, which provide a means to understand how human operators perceive the world around, then process that information and make decisions based on the knowledge that they already have and the projected knowledge of the reactions that will occur in the world in response to the actions the operator makes. Two major situation awareness methods will be used, GDTA as a means to discover the requirements the interface needs to solve, and SAGAT to conduct the evaluation on the three interfaces. This technique can isolate the differences an operator has in situation awareness when presented with relevant information given by each of the three interfaces that were built for this thesis. Where the first interface presents the information within the operator’s focal point of view in a pictorial style, the second interface shows the same information within the same point of view has the first interface but only shows it in a textual manner. While the third interface shows the relevant information in the operator’s peripheral field of view. Also SAGAT can provide insight on the question to know if providing the operator with feed-forward information about the stoppage distances of the bi-wheeled industrial hovercraft has any effect on the operator’s decision making.