Stepwise π-extension of double [5]helicene diimides to planar nanographene diimides

TL;DR

Scientists developed a new way to make helical and planar nanographene diimides with tunable light-emitting properties for use in optoelectronics.

Contribution

A stepwise synthetic route to produce double [5]helicene and planar nanographene diimides with high photoluminescence quantum yields.

Findings

The planar nanographene diimide achieved a photoluminescence quantum yield of 63% in solution.

The solid-state photoluminescence efficiency reached up to 32% for helical rylene diimides.

Molecular structure influences exciton dynamics and emission behavior, as shown by photophysical studies.

Abstract

A facile, stepwise synthetic route has been developed to access symmetric double [5]helicene diimides and their planar nanographene diimide counterparts via a C-shaped asymmetric [5]helicene. The synthetic strategy employs benzannulation and Scholl reaction methodologies to achieve progressive π-extension, yielding a new class of n-type rylene diimides with reversible redox characteristics. These helical and planar diimides exhibit variable crosswise π-conjugation and structural tunability, resulting in emission wavelengths that can be tailored alongside enhanced photoluminescence quantum yields—from 12% for the S-shaped diimide, to 57% for the C-shaped intermediate, and up to 63% for the fully planar nanographene diimide. Such properties make them promising candidates for quantum photonics, particularly as single-photon emitters. Photophysical properties, including time-resolved photoluminescence and transient absorption spectroscopy, reveal correlations between molecular structure, exciton dynamics, and emission behaviour. Notably, these helical rylene diimides demonstrate high photoluminescence efficiency in the solid state, reaching up to 32%, positioning them as strong contenders for next-generation optoelectronic devices.

Among double [n]helicenes, known for their simplicity and configurational stability when n exceeds 4, double [5]helicene imides remain underexplored. Here, the authors develop a stepwise synthetic route to access these diimides, as well as planar nanographene diimides via C-shaped mono-[5]helicene diimide, using benzannulation and Scholl reactions for progressive π-extension, reporting fluorescence quantum yields of up to 63% in solution and 32% in the solid state.

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