Anion-Directed Assembly of Atomically Precise Silver Nanofibers: Tunable Inner Diameters and Mechanical Exfoliation...

Nanofibrous architectures, a prominent class of one-dimensional nanomaterials, continue to captivate researchers in the exploration of novel nanofibrous materials and their diverse applications in nanotechnology. Creating crystalline nanofibers with inorganic walls capped by organic ligands is both critical and challenging, requiring precise structural control and consistent internal diameters. Herein, through anion-directed assembly, we demonstrate the controlled creation of semiconducting silver nanofibers with tunable and uniform internal diameters, exemplified by [V₃O₁₀@Ag₂₂(ⁱPrS)₁₄(CH₃COO)₂Cl]_n (Ag22-NF), [Cl₃@Ag₂₁(ⁱPrS)₁₄(PhCOO)₄]_n (Ag21-NF), and [Ag₆(ⁱPrS)₄(PhCOO)₂]_n (Ag6-NF). Importantly, Ag22-NF encapsulates V₃O₁₀^5- ions within a ∼ 6.52 Å diameter; Ag21-NF contains Cl^- and silver ions within a ∼ 5.69 Å diameter; and Ag6-NF is a hollow, template-free nanofiber with a diameter of ∼ 4.57 Å. These nanofibers were further fabricated through mechanical exfoliation of three distinct silver single crystals, preserving their well-ordered structural integrity and alignment with the bulk crystal architecture. As a concept-of-application, the field-effect transistor devices based on Ag6-NF exhibit high ratios of on to off current at ∼ 10⁴-10⁷, demonstrating the outstanding semiconducting performance. This work not only unveils a diverse array of connecting building units that generate nanofibers within three distinct assemblies but also elucidates the profound influence of template size on their optical properties, thereby exemplifying the intricacies of anion-directed design in controlled nanoscale synthesis.