Coronenes with push-pull geometries from macrocycle-forming Perkin condensations.

Area of Science:

• Organic Chemistry
• Supramolecular Chemistry
• Materials Science

Background:

• The Perkin reaction traditionally yields ester-substituted macrocycles with four or six building blocks.
• Two-element macrocycles, particularly those synthesized via the Perkin reaction, have remained a synthetic challenge.

Purpose of the Study:

• To develop a novel synthetic strategy for constructing two-element macrocycles.
• To explore the formation of macrocycles with specific geometries and functionalities.
• To investigate the subsequent transformation of these macrocycles into substituted coronenes.

Main Methods:

• Design and synthesis of a phenanthrene-derived building block with pincer-like glyoxylic acid substituents.
• Condensation of the phenanthrene unit with a complementary phenylenediacetic acid unit to form macrocycles.
• Photocyclisation of the synthesized cyclophanes to yield coronene derivatives.

Main Results:

• Successful formation of a two-block macrocycle using the novel phenanthrene building block.
• Incorporation of ether functionalities enhanced reaction yields and introduced push-pull geometries.
• Efficient photocyclisation of cyclophanes yielded tetra- and hexasubstituted coronenes.

Conclusions:

• A new method for synthesizing two-element macrocycles has been established, expanding the scope of Perkin reaction chemistry.
• The developed building blocks and methodology provide access to functionalized macrocycles and coronenes.
• This work opens avenues for creating novel conjugated systems with tailored electronic properties.