Hierarchical self-assemblies of carnosine asymmetrically functioned perylene diimide with high optoelectronic response

Hypothesis: Taking advantage of photoinduced electron transfer, one dimensional organic nanomaterials with tunable donor-acceptor (D-A) interface provide a promising avenue to get high optoelectric properties. However, strong charge transfer interaction between D and A segments impedes the formation of long-range ordered structure, which limits the charge transport through efficient π electronic delocalization. Incorporation of chiral peptide offering various hydrogen bonding (H-bonding) along with asymmetric molecular structure enables substantially controllable D-A interface and tunable organization of the π-conjugates.

Experiments: A new amphiphilic perylene diimide (CUPDI) with PDI as an acceptor is designed and synthesized. A polar chiral dipeptide composed of β-alanine and l-histidine with the imidazole ring as the donor i.e., l-carnosine, is incorporated at one of imides. Transition of various supramolecular assemblies of CUPDI is realized by changing CUPDI concentration and solvents. The photoelectronic properties of the assemblies are investigated as well as their association with the microstructure of the nanomaterials.

Findings: Delicately tuned hydrogen bonds between the peptides and π-π interaction between PDI cores in different solvents enable the formation of assemblies with multifarious microstructures such as small spherical aggregates, nanowires with uniform diameter, nanobelts, and irregular aggregates. The maximum amount of photocurrent enhancement is up to 1.08 µA observed for the nanobelt, four times higher than that of irregular aggregates. However, the nanowires show the best performance of 7.1-fold in response to ammonia. Thus, the photoelectric performances are strongly dependent on the the molecular arrangement within the nanomaterials.