Deep Molecular Orbital Driven High-Temperature Hydrogen Tautomerization Switching

Hydrogen tautomerization molecular switches, a promising class of molecular components for the construction of complex nanocircuits, have been extensively studied using low-temperature scanning tunneling microscopy. However, these molecules are generally only reliably controllable in cryogenic environments, obstructing their utility in real devices. Here, we use dispersion-inclusive density functional theory and systematically investigate the adsorption and tautomerization behaviors of porphycene on six transition-metal surfaces. Among these surfaces, we found that hydrogen tautomerization on the Pt(110) surface corresponds to the largest switching barrier, allowing a controllable transition at high temperature. The switching behavior is closely related to the exceptional degree of charge transfer in the HOMO-2 orbital, illustrating the important role of deep orbital-surface interactions in porphycene molecular switching. Our work provides an in-depth understanding of the porphycene tautomerization mechanism and highlights new research avenues toward the practical application of molecular switches.