Using scanning tunneling microscope break-junction experiments and a new first-principles approach to conductance calculations, we report and explain low-bias charge transport behavior of four types of metal-porphyrin-gold molecular junctions. A nonequilibrium Green's function approach based on self-energy corrected density functional theory and optimally tuned range-separated hybrid functionals is developed and used to understand experimental trends quantitatively. Importantly, due to the localized d states of the porphyrin molecules, hybrid functionals are essential for explaining measurements; standard semilocal functionals yield qualitatively incorrect results. Comparing directly with experiments, we show that the conductance can change by nearly a factor of 2 when different metal cations are used, counter to trends expected from gas-phase ionization energies which are relatively unchanged with the metal center. Our work explains the sensitivity of the porphyrin conductance with the metal center via a detailed and quantitative portrait of the interface electronic structure and provides a new framework for understanding transport quantitatively in complex junctions involving molecules with localized d states of relevance to light harvesting and energy conversion.

Molecular junctions formed using the scanning-tunneling-microscope-based break-junction technique (STM-BJ) have provided unique insight into charge transport at the nanoscale. In most prior work, the same metal, typically Au, Pt, or Ag, is used for both tip and substrate. For such noble metal electrodes, the density of electronic states is approximately constant within a narrow energy window relevant to charge transport. Here, we form molecular junctions using the STM-BJ technique, with an Au metal tip and a microfabricated graphite substrate, and measure the conductance of a series of graphite/amine-terminated oligophenyl/Au molecular junctions. The remarkable mechanical strength of graphite and the single-crystal properties of our substrates allow measurements over few thousand junctions without any change in the surface properties. We show that conductance decays exponentially with molecular backbone length with a decay constant that is essentially the same as that for measurements with two Au electrodes. More importantly, despite the inherent symmetry of the oligophenylamines, we observe rectification in these junctions. State-of-art ab initio conductance calculations are in good agreement with experiment, and explain the rectification. We show that the highly energy-dependent graphite density of states contributes variations in transmission that, when coupled with an asymmetric voltage drop across the junction, leads to the observed rectification. Together, our measurements and calculations show how functionality may emerge from hybrid molecular-scale devices purposefully designed with different electrodes beyond the so-called "wide band limit," opening up the possibility of assembling molecular junctions with dissimilar electrodes using layered 2D materials.