Fine-Tuned Nanostructures Assembled from l-Lysine-Functionalized Perylene Bisimides

Abstract

Controllable nanostructures with tunable dimensions were obtained via self-assembly of CBZ-L-lysine-functionalized tetrachloroperylene bisimides (4ClPBI-Lys). Depending on the nature of substitute, solvent polarity, and sample concentration, 4ClPBI-Lys could form nanosphere, nanowire, nanobelt, and nanosheet, which were found to have different degree of molecular ordering. The effects of substitution position with respect to L-lysine on 4ClPBI were also explored in terms of assembly nanostructures. Hydrogen bonding was important to promote formation of long-range ordering. The nanostructures of different assemblies were characterized using SEM, TEM, XRD, UV-vis, and FTIR spectroscopy. For each obtained supramolecular assembly, we also found that the molecular packing motif ultimately determined the corresponding devices' electronic properties.

Morphogenesis and Optoelectronic Properties of Supramolecular Assemblies of Chiral Perylene Diimides in a Binary Solvent System

“…2a). Similar changes were seen for other PDI derivative aggregates, which tended to self-assemble into ordered structures because of the strong π–π interaction between the perylene cores 30, 31 . According to time-dependent SEM analysis at an f w of 60%, CPDI-Ph showed metastable nanobelts in freshly sample, forming gradually well-defined nanobelts in 3 min, and the nanobelts elongated over time (Figs 2c–f and S4).…”

“…As a result, at an f w of 60%, thermodynamic factors dominated the self-assembly and preferentially formed highly ordered nanostructures to minimize the free energy of the system. With an increase of water content, solvent became more unfavorable for reassembly, therefore, the CPDI-Ph molecules aggregated too fast to adjust their optimal conformation 31 . Therefore, at an f w of 90%, the nucleation dominated the assembly growth, and kinetically favored nanostructures were obtained.…”

“…The electronic properties of the supramolecular assemblies of L -lysine-functionalized 4ClPDI were also related to their molecular packing, which was tailored using various assembly strategies 31 . However, to the best of our knowledge, this is the first reported investigation of the field-effect mobility of OFETs based on the morphology of self-assembled chiral PDI semiconductors.…”

Self-Assembly of Perylene Imide Molecules into 1D Nanostructures: Methods, Morphologies, and Applications

“…The well-ordered π−π stacking structures and the existence of carboxyl acid and hydroxyl moieties in the side-chains provide the possibility of self-doping and are believed to play a crucial role in the excellent conductive properties of 1D nanofibers of these amphiphilic PDIs ( Figure 11). 49 For rigid molecules bearing bulky and twisted moieties both at imide and at bay positions, evaporation-triggered in situ self-assembly on substrates seems to be a preferred method. For example, the b4 molecule modified with a bulky p-type tetraphenylethenyl group ( Figure 8) has been successfully self-assembled into well-organized 1D nanofibers by slowly evaporating the solvents from H 2 O/THF, CH 3 OH/CH 2 Cl 2 , hexane/CH 2 Cl 2 , or CH 3 OH/dioxane mixtures.…”

Self-assembly of chiral amphiphiles with π-conjugated tectons

“…Therefore, advances in the development of new type of chiral amphiphiles will not only enrich the family of conventional amphiphiles that are based on covalent bonds but will also provide a new kind of building block for the preparation of complex self-assemblies. In particular, various examples of chiral molecules with extended -conjugated ring systems, such as hexabenzocoronenes [54,55], perylene bisimides (PTCDI) [56][57][58], and oligothiophene [59], porphyrin [60,61] and 1,1′-binaphthyls [62] have been reported to form -stacks with helical supramolecular structures that exhibit some novel physical and chemical properties.…”