A Self‐Assembly Phase Diagram from Amphiphilic Perylene Diimides

Abstract

Supramolecular forces govern self-assembly and further determine the final morphologies of self-assemblies. However, how they control the morphology remains hitherto largely unknown. In this paper, we have discovered that the self-assembled nanostructures of rigid organic semiconductor chromophores can be finely controlled by the secondary forces by fine-tuning the surrounding environments. In particular, we used water/methanol/hydrochloric acid to tune the environment and observed five different phases that resulted from versatile molecular self-assemblies. The representative self-assembled nanostructures were nanotapes, nanoparticles and their 1D assemblies, rigid microplates, soft nanoplates, and hollow nanospheres and their 1D assemblies, respectively. The specific nanostructure formation is governed by the water fraction, R(w), and the concentration of hydrochloric acid, [HCl]. For instance, nanotapes formed at low [HCl] and R(w) values, whereas hollow nanospheres formed when either the HCl concentration is high, or the water fraction is low, or both. The significance of this paper is that it provides a useful phase diagram by using R(w) and [HCl] as two variables. Such a self-assembly phase diagram maps out the fine control that the secondary forces have on the self-assembled morphology, and thus allows one to guide the formation toward a desired nanostructure self-assembled from rigid organic semiconductor chromophores by simply adjusting the two key parameters of R(w) and [HCl].

A Potential Perylene Diimide Dimer‐Based Acceptor Material for Highly Efficient Solution‐Processed Non‐Fullerene Organic Solar Cells with 4.03% Efficiency

“…Perylene diimides (PDIs) are n‐type organic semiconductors with high chemical, thermal, and light stabilities . They generally show a strong absorption band in the visible region with a maximum molar extinction coefficient ( ε max ) on the order of 10 4 M −1 cm −1 , good electron‐accepting ability due to the well‐placed LUMO energy, ca. −4.0 eV, and excellent electron mobility on the order of 10 1 –10 −3 cm 2 V −1 s −1 .…”

“…−4.0 eV, and excellent electron mobility on the order of 10 1 –10 −3 cm 2 V −1 s −1 . [7c,] Their solubility and optoelectronic and self‐assembling properties may be fine‐tuned by tailoring the substituted groups on the imide‐N, bay‐ (e.g., 1,6,7,12), and/or 2,5,8,11 positions . So, PDIs are promising candidates as non‐fullerene acceptor materials and this has been researched for several decades .…”

Novel EDTA-ligands containing an integral perylene bisimide (PBI) core as an optical reporter unit

“…11 PBIs are usually insoluble in water. Therefore, several attempts have been performed in order to increase their solubility in aqueous media, either with functionalization in the bay region [12][13][14][15][16] or at the side imide groups. [17][18][19][20][21][22][23][24][25] Recently, we have introduced a series of highly water-soluble PBIs containing anionic (R 1 ) or cationic (R 2 ) Newkome dendronized substituents -representative examples are given in Fig.…”

Amphiphilic Ionic Perylenediimides: Structures, Self-Assembly Studies and Biomedical Applications

“…Yao and co-workers [35] synthesized a PID derivative with pyridyl in the bay region. They found that the self-assembly of amphiphilic AIPDI 4 ( Figure 6) can be subtly controlled by tuning the environmental parameters.…”