Abstract: According to Moore’s Law, the next frontier in electronics technology is creating electrical components on the nanoscale level. This is the regime of single molecules which can be tailored in size and structure through synthetic chemistry methods. However, interface effects play an outsized role in determining electronic properties of a single molecule bound to metal electrodes. A detailed understanding of atomic arrangements, charge transfer and electron transport at the metal-molecule junction is required to make progress in this field. In this talk I will give an overview of my lab’s approaches to probing sub-nanometer atomic arrangements in such single molecule systems and correlating them to electronic properties. We combine experimental measurements using the Scanning Tunneling Microscope-based Break Junction approach and computational Density Functional Theory techniques. I will describe our recent progress in identifying formation and evolution of single molecule junctions containing transition metal centers. Such junctions can increase the scope of observable phenomena due to incorporation of metal centers with new degrees of freedom. Interestingly, we find that transition metal atoms can be wired into single molecule junctions in situ, during junction elongation, using anionic linker groups. These results provide insights into interface phenomena and help identify successful strategies for incorporating molecular and low dimensional materials into next generation electronics or energy devices.