Phthalocyanine-Triggered Helical Dipeptide Nanotubes with Intense Circularly Polarized Luminescence

Small. 2022 Jan;18(4):e2104438. doi: 10.1002/smll.202104438. Epub 2021 Nov 23.

Abstract

Nanotubes with circularly polarized luminescence (CPL) are attracting much attention due to many potential applications, such as chiroptical materials, displays, and sensing. However, it remains a challenge to change the assemblies of ordinarily molecular building blocks into CPL supramolecular nanotubes. Herein, the regulation of quite common dipeptide (Fmoc-FF) assemblies into unprecedented helical nanotubes exhibiting intense CPL is reported by simply doping a few phthalocyanine (octakis(carboxyl)phthalocyaninato zinc complex (Pc)) molecules. Interestingly, altering the Fmoc-FF/Pc molar ratios over a wide range cannot change the nanotubes structures according to transmission electron microscopy (TEM) and atomic force microscope (AFM) measurements. Although molecular dynamics simulations suggest that the noncovalent interactions between Fmoc-FF and Pc are quite weak, few Pc molecules can still change the secondary structures of a large number of Fmoc-FF assemblies, which hierarchically form helical supramolecular nanotubes with long-range ordered molecular packing, leading to intense CPL signals with large luminescence dissymmetry factor (glum = 0.04). Consequently, the chiral reorganization of Fmoc-FF assemblies is dependent on the coassembly between Pc molecule and Fmoc-FF supramolecular architectures. These results open the possibility for the fine-tuning of helix and supramolecular nanotubes with CPL properties by using a small number of cofactors.

Keywords: circularly polarized luminescence; dipeptides; nanotubes; phthalocyanines; supramolecular assembly.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Dipeptides
  • Indoles
  • Isoindoles
  • Luminescence*
  • Nanotubes*

Substances

  • Dipeptides
  • Indoles
  • Isoindoles
  • phthalocyanine