Healable Supramolecular Polymers as Organic Metals

Abstract

Organic materials exhibiting metallic behavior are promising for numerous applications ranging from printed nanocircuits to large area electronics. However, the optimization of electronic conduction in organic metals such as charge-transfer salts or doped conjugated polymers requires high crystallinity, which is detrimental to their processability. To overcome this problem, the combination of the electronic properties of metal-like materials with the mechanical properties of soft self-assembled systems is attractive but necessitates the absence of structural defects in a regular lattice. Here we describe a one-dimensional supramolecular polymer in which photoinduced through-space charge-transfer complexes lead to highly coherent domains with delocalized electronic states displaying metallic behavior. We also reveal that diffusion of supramolecular polarons in the nanowires repairs structural defects thereby improving their conduction. The ability to access metallic properties from mendable self-assemblies extends the current understanding of both fields and opens a wide range of processing techniques for applications in organic electronics.

Induction and control of supramolecular chirality by light in self-assembled helical nanostructures

“…1). This observation, consistent with the literature [20][21][22]29 , indicates that a small number of triphenylammonium radicals were generated by light exposure and triggered stacking of the TPA moieties with the aid of amide hydrogen bonding. Chlorinated solvents seem to play an important role in the radical generation process, as solvent radicals are easily formed by light exposure, and reversibly transfer electrons to the TPA moiety.…”

“…The existence of amide hydrogen bonding was also observed in our system by attenuated total reflection infrared spectroscopy of 1 after light irradiation and evaporation of solvent ( Supplementary Fig. 4) 22,30,31 .…”

“…As a key molecular motif for the light-induced self-assembly process, we use a triphenylamine (TPA) moiety that contains three phenyl rings connected to a central nitrogen atom similar to the blades of a propeller. TPA-containing molecules have been shown to selfassemble on light exposure in chlorinated solvents by the formation of triphenylammonium radicals that adopt more planar configurations than the neutral forms and facilitate stacking [19][20][21][22][23] . Simply by employing CPL as a light source in the self-assembly process of a TPA-containing molecule, we show that self-assembled aggregates with supramolecular chirality can be generated, driven by the helical stacking of the TPA moieties.…”

Supramolecular Electropolymerization

“…By assuming the number of wires in the electrodes,and by assuming all of them being connected, we can estimate aminimum value as high as 0.56 cm 2 V À1 s À1 , close to the theoretical prediction published in the literature. [9,10,20] In conclusion, we have described the first example of what can be defined as a" supramolecular electropolymerization" process.Itrepresents anew tool of fundamental and practical interest for supramolecular chemistry in general. [9,10,20] In conclusion, we have described the first example of what can be defined as a" supramolecular electropolymerization" process.Itrepresents anew tool of fundamental and practical interest for supramolecular chemistry in general.…”

Self‐Healing Materials for Next‐Generation Energy Harvesting and Storage Devices

“…Besides the N-heterocyclic carbene-metal complexes, Giuseppone' group described a new class of healable supramolecular polymers as organic metals based on photo induced through-space charge-transfer complexes. [102] The one-dimensional supramolecular nanowires self-assembled by tris-amide triarylamines displayed similar charge-transport feature to that observed in metallic conducting conjugated polymers, thus exhibited electrical conductivity. More importantly, the diffusion of the light-induced supramolecular polarons in the nanowires repaired structural defects (i.e., lateral or rotational misalignments of the stacks) effectively under a quite short of pulse of light (15 s).…”