Electric-Field-Induced Tautomerism in Metal-Free Benziporphyrins Enables Aromaticity-Controlled Conductance Switching

Abstract

Metal-free porphyrins can switch between hydrogen-bonded tautomers, potentially enabling reversible control in molecular electronics. However, electric field gating of porphyrin tautomerism, which is critical for device integration, has not been fully realized. We propose metal-free benziporphyrins (MFBPs), in which one pyrrole ring is replaced with a phenol group, as a new platform for tautomer-based molecular electronics. This approach introduces asymmetry, which allows for three distinct tautomers, each possessing a characteristic aromatic or antiaromatic electronic structure. Density functional theory and quantum transport calculations show that: i) experimentally realisable electric fields can selectively stabilize each tautomer, and ii) each tautomer exhibits a characteristic conductance profile. The strong switching capability of MFBPs is demonstrated by ON/OFF ratios exceeding 500 at low bias. Fused MFBPs further expand functionality by providing multiple tautomeric states for multistate molecular registers and enabling wire-like architectures with enhanced conductance. These results establish MFBPs as versatile building blocks for electric-field-responsive molecular devices and open new research opportunities for molecular-scale logic and memory.