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CC BY 4.0 · Organic Materials 2024; 06(02): 33-39
DOI: 10.1055/a-2291-8673
Soluble Graphene Nanoarchitectures
Original Article

Diazananographene with Quadruple [5]Helicene Units: Synthesis, Optical Properties, and Supramolecular Assembly

Xiao-Hui Ma 
a   State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. of China
,
Jiang-Feng Xing 
a   State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. of China
,
Ling Chai 
a   State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. of China
,
Qing-Song Deng 
a   State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. of China
,
Xuan-Wen Chen 
a   State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. of China
,
Hai-Feng Su 
a   State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. of China
,
Chao Li 
b   SINOPEC Maoming Company,Maoming 525000, P. R. of China
c   Beijing University of Chemical Technology, Beijing, 100000, P. R. of China
,
Yuan-Zhi Tan 
a   State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. of China
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Abstract

A helical diazananographene (1) was successfully synthesized by employing sterically hindered t-butyl groups to inhibit further dehydrocyclization of [5]helicene units. These t-butyl groups stabilized the conformation of [5]helicene units, thus resulting in three stable conformers of 1, comprising a pair of enantiomers (1-(P, P, P, P) and 1-(M, M, M, M)) and a mesomer (1-(P, P, M, M)). In comparison to its planar analogs, helical 1 exhibited broadened peaks in both its absorption and emission spectra, leading to an increase in the emission quantum yield from 0.3 to 0.6. The significantly enhanced radiative decay rate (k r) accounted for the increase in the quantum yield of 1. Additionally, it was observed that the compound could be fully protonated upon the addition of an equivalent acid. Furthermore, 1 assembled into a chiral trimeric metallosupramolecular complex upon coordination with the PdII units. Both protonated 1 and the metallosupramolecular complex exhibited an enhanced circular dichroic response. These findings revealed that the incorporation of a helical structure and pyridinic nitrogen-doping into the nanographene can allow the synthesis of responsive chiroptical graphenic materials, which could serve as fundamental components for constructing chiral hierarchical metallosupramolecular structures.

Key words

diazananographene - [5]helicene - optical properties - supramolecular assembly

Supporting Information



Publication History

Received: 31 December 2023

Accepted after revision: 14 March 2024

Accepted Manuscript online:
20 March 2024

Article published online:
30 April 2024

© 2024. The Authors. This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting unrestricted use, distribution, and reproduction so long as the original work is properly cited. (https://creativecommons.org/licenses/by/4.0/).

Georg Thieme Verlag KG
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