ИСТИНА

Fabrication of processable one-dimensional (nano)semiconductors and their arrangement on solids are among major challenges for organic electronics. Supramolecular aggregation of aromatic disсotics such as phthalocyanines have gained attention as a strategy for creating tubular nanostructures in a controlled fashion but their electric properties remain relatively low. Herein, we describe cooperative self-assembly of lutetium crown-substituted double-decker phthalocyaninate (LuL2) via crown-assisted coordination with K+ for fabricating supramolecular nanowires with an average length up to 50 µm, thickness down to 5 nm. The conductivity of the film obtained with deposition of nanowires from the dispersion in chloroform under slow evaporation of the solvent is 11.4 S•cm-1. This value is the highest measured in non-doped phthalocyanine assemblies. The ability of crown-groupes of the LuL2 complex to interact with K+ ions dictate the full conjugation of macrocyclic rings of phthalocyanine complexes in 1D aggregate and the efficiency of charge transfer along the nanowires. The high sensitivity of K+-LuL2 assemblies to the electric field makes it possible to use field-assisted method for the arrangement of the already prepared nanowires on solid supports. The voltage applied between the electrodes guides the oriented deposition of the already formed nanowires from their solution onto the surface. The nanowires are oriented along the field lines from anode to cathode immediately after field switch on. The deposition proceeds within 20 minutes yielding the continuously ordered layer of nanowires on the support. The packing density of the nanowires within the layer can be tuned by varying the concentration of K+-LuL2 dispersion. The recyclability of the self-assembled nanowires is a significant advantage over conventional covalently linked polymers for fabricating organic-based devices for a next-generation “green” electronics. The K+-LuL2 nanowires, otherwise stable in water and most organic solvents, can be easily disintegrated into starting components in acetonitrile and then separatied for further re-application without adding any other chamicals. Our results demonstrate the potency of supramolecular strategy based on self-assembly for fabricating semiconductor nanowires with high electric properties from organic molecules with large aromatic system, such as phthalocyanines. Cooperative process involving weak intermolecular oordination bonds provide full conjugation of electronic systems of phthalocyanines for efficient charge transfer along nanowires. Although the cooperative binding provides stability to the as-formed structures, the bond weakness makes it possible to desintegrate these nanowires in a good aprotic solvent for further recycling.