The construction of mechanically interlocked molecules has been the subject of decades of research. The efficiency of strategies for preparing these molecules has increased continuously. In recent years, the transition metal templation strategy has played quite a remarkable role in the synthesis of entwined or mechanically bonded structures due to the metals’ diverse coordination chemistry and ability to chelate ligands. In the early stages of this method’s development, the metal ions were used as integral part of the scaffold for such components as rings and stoppers to generate the interlocked structures. In newly developed active metal templation strategies, metal ions are used to promote covalent bond forming reactions while simultaneously acting as structural supports. In this thesis, three main aspects are expanded for the discussion of the application of metal template strategies. First of all, the newly developed strategy - active metal template - will be described and exemplified using the Huisgen-Meldal-Fokin Cu(I)- catalyzed 1,3-cycloaddition of azides with terminal alkynes (the CuAAC “click” reaction), the Cu(I)-mediated Cadiot-Chodkiewicz heterocoupling of an alkyne halide with a terminal alkyne, and the Ni(II)-catalyzed Csp3-Csp3 homocoupling reaction. Secondly, the thesis discusses the use of these strategies to obtain several hard-to-access structures, including the first high-yielding doubly threaded [3]rotaxanes, heterocircuitcatenanes and the one pot synthesis of homocircuit-catenanes, and the smallest molecular trefoil knot prepared to date. Lastly, as an extension of the metal temptation strategy, the final chapter of this thesis will discuss the assembly of inorganic metal-organic catenanes by metal coordination.

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This thesis explores the surface assembly of mechanically interlocked molecular architectures at gold surfaces for potential applications in molecular switches, anion sensing and stimuli (redox and optical) responsive molecular films. <b>Chapter One</b> introduces the field of mechanically interlocked molecules focusing on rotaxane and catenane surface assemblies in the form of single molecule thick self-assembled monolayers. A review of the surface-attached characteristics of mechanically interlocked molecules is given before exploring specific anion template directed strategies for their construction. The potential to incorporate both redox-active and optically-active functional groups within these mechanically interlocked molecules is also discussed. <b>Chapter Two</b> provides the experimental details and procedures employed in this thesis to characterise the molecular systems under investigation. <b>Chapter Three</b> introduces several surface characterisation techniques such as; ellipsometry, contact angle, X-ray reflectivity and X-ray photoelectron spectroscopy, with a particular focus of applying these tools to probe the surface co-conformation of switchable and interlocked molecules at surfaces. Electroanalytical techniques such as cyclic voltammetry, chronoamperometry and electrical impedance spectroscopy are also introduced. <b>Chapter Four</b> details the surface assembly of a series of ferrocene containing anion templated catenane self-assembled monolayers on gold. Detailed electrochemical and angle resolved X- ray photoelectron spectroscopy characterisation elucidates the co-conformation upon surface attachment. <b>Chapter Five</b> details the anion templated surface assembly of a redox-active rotaxane self- assembled monolayer on gold. Subsequent electroanalysis and X-ray photoelectron spectroscopy characterisation confirms the structural integrity of the film and a possible co- conformation at the surface is discussed. <b>Chapter Six</b> describes efforts towards constructing optically responsive hybrid d-f lanthanide containing mechanically interlocked molecules. Initial work focuses on switching characteristics of a redox switchable antennae and its ability to modulate the luminescence of a series of lanthanide complexes in solution. Subsequent surface attachment of the lanthanide complexes in the form of emissive self-assembled monolayers is also investigated.

I rotaxaner följs förflyttningen av makrocykeln vanligtvis med 1H-NMR spektroskopi. Målet med detta projekt är i stället att utveckla ett system som möjliggör att förflyttningen av makrocykeln kan observeras med hjälp av luminiscerande lantanid emission. Detta bör vara ett kraftfullt verktyg, då luminiscerande emission skulle möjliggöra att makrocykelns position längs med tråden kan avläsas direkt med blotta ögat. För att lantanid-baserade system ska kunna luminiscera krävs det att en aktiverande antennmolekyl finns i närheten av lantaniden. I detta projekt placerades en lantanidligand i den ena stoppande änden av en [2]rotaxan och en antennmolekyl sattes på den trådade makrocykeln. En förändring av pH:t medför att makrocykeln förflyttas närmre till lantanidliganden, vilket i sin tur medför att antennen aktiverar lantaniden och den luminiscerande emissionen startar. Baserat på styrkan av luminiscensen bör man då kunna avgöra makrocykelns position i rotaxanen. I framtiden hoppas vi kunna använda detta visualiseringsverktyg för att kunna börja använda rotaxaner som biosensorer för medicinsk diagnostik. / In rotaxanes, the movement of the macrocycle is usually tracked using 1H-NMR spectroscopy. The goal of this project is to instead develop systems so one can follow the macrocycle movement through luminescent lanthanide emission. This should be a powerful tool, as luminescence emission would allow for a direct visual readout of the macrocycle position along the thread with the naked eye. To allow luminescence in lanthanide-based systems, a sensitizing antenna molecule needs to be present in close proximity to the lanthanide. In this project, a lanthanide ligand was placed at the stoppered end of a [2]rotaxane, and a sensitizing antenna was attached to the threaded macrocycle. A change in pH induces the macrocycle to move closer to the lanthanide stopper, which causes the antenna to sensitize the lanthanide and start the luminescence emission. Based on the strength of the luminescence, one should then be able to determine the location of the macrocycle in the rotaxane. We hope to use this visual readout tool to eventually turn rotaxanes into useful point-of-care biosensors for medical diagnostics.