Polycyclic- and sulfurcontaining-compounds: from polycyclic hydrocarbons to thiaspherophane

This thesis contains the examination of four, in first glance, unrelated topics. However, the overarching motivation behind these subjects are the same: The Art and Challenge of Organic Chemistry.
I. The first chapter deals with the design, based on theoretical principles, and preparation of unsaturated spirocyclic compounds bearing sulfur functionalities with the aim of elucidating the charge-transport properties of such molecules on the level of single molecules. In collaboration with the Group of Professor Herre van der Zant from the Delft University of Technology preliminary conductance measurements of such spirocyclic structures could be gathered. The motivation for this joint endeavor is the prospect of using such spirocyclic structures as a molecular switch for the construction of molecular electronic devices.
II. The second part shows our engagement in the long tradition among organic chemist to challenge our abilities to synthesize inspiring, complex and aesthetical pleasing structures. One such structure was identified by employing predictive computational methods by the group of Professor Jean-Louis Reymond. The structure of interest was recognized as one of the last three remaining and not yet synthesized fully-cyclic C11 isomers without strain. Encouraged by this finding, we accepted the challenge to synthesize this tetracyclic saturated hydrocarbon with the molecular formula C11H16 with the proposed trivial name of trinorbornane.
III. Thirdly, Thiaspherophane: A highly symmetrical structure consisting of eight benzene rings bridged over twelve sulfur atoms describing a cuboctahedron: one of the 13 Archimedean solids. This elusive molecule, predicted over 25 years ago, bears the potential of being transformed into a cryptatium. Our efforts and progress on the synthesis of thiaspherophane will be discussed.
IV. Unsymmetrical disulfides are ubiquitous in the field of chemistry and at the interface with physics, where nanotechnology emerges. In this chapter, our investigation of an efficient method for the preparation of unsymmetrical disulfides will be presented Whereby the potential of this method for the formation of functional units bearing multiple unsymmetrical disulfides was assessed with the aim of using these compounds for functionalization of gold surfaces.