Coaxially Conductive Organic Wires Through Self-Assembly

Abstract

Here, we describe the synthesis of the hexameric macrocyclic aniline (MA­[6]), which spontaneously assembles into coaxially conductive organic wires in its oxidized and acidified emeraldine salt (ES) form. Electrical measurements reveal that ES-MA­[6] exhibits high electrical conductivity (7.5 × 10–2 S·cm–1) and that this conductivity is acid–base responsive. Single-crystal X-ray crystallography reveals that ES-MA­[6] assembles into well-defined trimeric units that then stack into nanotubes with regular channels, providing a potential route to synthetic nanotubes that are leveraged for ion or small molecule transport. Ultraviolet–visible–near-infrared absorbance spectroscopy and electron paramagnetic spectroscopy showcase the interconversion between acidic (conductive) and basic (insulating) forms of these macrocycles and how charge carriers are formed through protonation, giving rise to the experimentally observed high electrical conductivity.

Design and Synthesis of New Type of Macrocyclic Architectures Used for Optoelectronic Materials and Supramolecular Chemistry

“…developed a hexameric macrocyclic aniline 8 and the acidified emeraldine salt ES‐8 (Figure 6). [20] The crystal devices of ES‐8 were fabricated on Si/SiO 2 wafers and exhibited higher conductivity value up to 7.5×10 −2 S/cm −1 (Figure 6B). Single‐crystal X‐ray diffraction of ES‐8 revealed that macrocycles could assemble into trimers in the solid state.…”

“…Photo inset visually demonstrates the color difference between acidified ES‐8 (right) and basified ES‐8 (left). Reproduced with permission [20] . Copyright 2023, American Chemical Society.…”

“…Evans and Nuckolls et al developed a hexameric macrocyclic aniline 8 and the acidified emeraldine salt ES-8 (Figure 6). [20] The crystal devices of ES-8 were fabricated on Si/SiO 2 and 3 (orange) in CH 2 Cl 2 (1.0×10 À 5 M). Inset: Luminescence photographs of 2 (left) and 3 (right) in CH 2 Cl 2 .…”

“…Reproduced with permission. [20] Copyright 2023, American Chemical Society. organoboranes have been employed as sensing materials to respond the presence of these anions.…”

Designing Long and Highly Conducting Molecular Wires with Multiple Nontrivial Topological States

“…35 In these wires, the topological and trivial structural limits can be controlled by the acidity of the environment because neutral amines are basic and the radical cations are acidic. 16 For C2[m], we envision that the nitrogen-containing molecules, which have been recently synthesized 36 but not studied as single-molecule circuits, could show novel conductance−length properties.…”