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Synfacts 2023; 19(09): 0871
DOI: 10.1055/s-0042-1751977
Synthesis of Materials and Unnatural Products

Molecular Cage from Diradical Dimerization

Contributor(s):
Dahui Zhao
,
Lihui Guo
Fuchs K, Rivero SM, Weidlich A, Rominger F, Israel N, Popov AA, Dreuw A, *, Freudenberg J, *, Casado J, *, Bunz UH. F. * Ruprecht-Karls-Universität, Heidelberg, Germany and University of Málaga, Spain
Dimerization of a Reactive Azaacene Diradical: Synthesis of a Covalent Azaacene Cage.

Angew. Chem. Int. Ed. 2023;
62: e202305712
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Key words

diradical dimerization - molecular cage - quinoid - dithienodiazaacene

Significance

Two series of regio-isomeric dicyanomethylene-substituted dithienodiazaacenes are synthesized. Different orientations of the thiophene units are found to bring about different diradical character and chemo-stability. The para-isomers are stable, closed-shell quinoidal molecules, while the ortho-isomer dimerizes into a cage-like structure, presumably via the open-shell diradical state.


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Comment

Uniquely, instead of forming covalent bonds directly between the radical sites mainly located with the dicyanomethylene carbons, the dimerization occurs by joining the ethynylene carbon adjacent to TIPS with the dicyanomethylene. This phenomenon suggests the diradicaliod character of the bis(TIPS-ethynylene)-substituted diazatetracene.


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Publication History

Article published online:
16 August 2023

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