Two-Dimensional Nanoarchitectonics of End-on Oligomers with Versatile Structures and Tunable Negative Differential Resistance

Maximizing the molecular information density requires simultaneously functionalizing distinct monomers and their coupling connections. However, current synthesis generally focuses on distinct monomers rather than coupling reactions because the multistep reactions significantly escalate the synthetic complexity in an exponential increase. Here, we report the two-dimensional nanoarchitectures (2DNs) of end-on oligomers, with versatile molecular structures and negative differential resistance (NDR), synthesized by programmed and surface-initiated step electrosynthesis based on the simultaneous utilization of six reactions including cross- and homocouplings. The resulting vertically end-on oligomers, with similar values in thickness and molecular length, as crystalline 2DNs, exhibit subnanometer uniformity, ultrahigh compressive modulus of 40 GPa, and low-bias NDR at 0.13 V with an ultralow power consumption of down to 0.05 nW/μm². This highly controlled electrosynthesis provides a unique dimension to enhance the structural diversity of molecular 2D nanomaterials for high-density and low-power consumption electronics.