Bonding-Directed Crystallization\nof Ultra-Long One-Dimensional\nNbS<sub>3</sub> van der Waals Nanowires

The rediscovery of\none-dimensional (1D) and quasi-1D\n(q-1D) van\nder Waals (vdW) crystals ushered the realization of nascent physical\nproperties in 1D that are suitable for applications in photonics,\nelectronics, and sensing. However, despite renewed interest in the\ncreation and understanding of the physical properties of 1D and q-1D\nvdW crystals, the lack of accessible synthetic pathways for growing\nwell-defined nanostructures that extend across several length scales\nremains. Using the highly anisotropic 1D vdW NbS<sub>3</sub>–I\ncrystal as a model phase, we present a catalyst-free and bottom-up\nsynthetic approach to access ultralong nanowires, with lengths reaching\nup to 7.9 mm and with uniform thicknesses ranging from 13 to 160 nm\nbetween individual nanowires. Control over the synthetic parameters\nenabled the modulation of intra- and interchain growth modalities\nto selectively yield only 1D nanowires or quasi-2D nanoribbons. Comparative\nsynthetic and density functional theory (DFT) studies with a closely\nrelated nondimerized phase, ZrS<sub>3</sub>, show that the unusual\npreferential growth along 1D can be correlated to the strongly anisotropic\nbonding and dimeric nature of NbS<sub>3</sub>–I.