Developing negative differential resistance (NDR) devices that simultaneously exhibit high conductance and a large peak-to-valley current ratio (PVCR) remains a critical challenge for the realization of molecular-scale logic circuits. The electronic transport properties of 4,4'-(pyrene-1,6-diylbis(ethyne-2,1-diyl)) dianiline (PDE) molecular devices were studied using density functional theory combined with first-principles calculations using non-equilibrium Green’s functions, exploring the regulatory mechanism of electrode materials and anchoring groups on NDR effects. We first fully optimized the geometric structure of isolated molecules and electrode cells, with the convergence criterion for the residual force on each atom set to less than 0.02 eV/Å. Exchange and correlations were described by the Perdew-Burke-Ernzerhof (PBE) functional within the generalized gradient approximation (GGA). The research results indicate that PDE molecular devices using gold electrodes have a continuous and high density of states, and strong hybridization with molecular orbitals leads to broadening of the transport peak, resulting in only monotonically increasing current-voltage characteristics. Due to the low density of states near the Fermi level, PDE molecular devices using zigzag graphene nanoribbon (ZGNR) electrodes do not induce hybridization or broadening of molecular orbitals, maintaining a sharp resonance state and achieving significant NDR effects. Changes in interface coupling caused by anchoring groups can regulate the alignment relationship between frontier molecular orbitals and the electrode Fermi level, playing a decisive role in the NDR effect. The amide group forms strong π-π conjugated coupling with the molecular skeleton and the ZGNR electrode through carbonyl groups, constructing efficient and continuous electron transport channels. In contrast, the amino anchoring group triggers destructive interference at the coupling interface between the molecule and the electrode, significantly reducing the device conductivity and resulting in substantial attenuation of the peak current. These findings deepen our understanding of the quantum transport mechanism at carbon-based molecular interfaces and provide clear theoretical guidance and material design paradigms for the future development of low-power, high-performance molecular switches, logic gates, and high-frequency oscillators.