Bottom-up Solution Synthesis of Graphene Nanoribbons with Precisely Engineered Nanopores

Wenhui Niu; Yubin Fu; Gianluca Serra; Kun Liu; Jörn Droste; Yeonju Lee; Zhitian Ling; Fugui Xu; José D Cojal González; Andrea Lucotti; Jürgen P Rabe; Michael Ryan Hansen; Wojciech Pisula; Paul W M Blom; Carlos-Andres Palma; Matteo Tommasini; Yiyong Mai; Ji Ma; Xinliang Feng

doi:10.1002/anie.202305737

Bottom-up Solution Synthesis of Graphene Nanoribbons with Precisely Engineered Nanopores

Angew Chem Int Ed Engl. 2023 Aug 28;62(35):e202305737. doi: 10.1002/anie.202305737. Epub 2023 Jul 18.

Authors

Wenhui Niu^{1

2

3}, Yubin Fu^{1

2}, Gianluca Serra⁴, Kun Liu², Jörn Droste^{5

6}, Yeonju Lee⁷, Zhitian Ling⁸, Fugui Xu³, José D Cojal González⁷, Andrea Lucotti⁴, Jürgen P Rabe⁷, Michael Ryan Hansen⁵, Wojciech Pisula^{8

9}, Paul W M Blom⁸, Carlos-Andres Palma^{7

10}, Matteo Tommasini⁴, Yiyong Mai³, Ji Ma^{1

2}, Xinliang Feng^{1

2}

Affiliations

¹ Max Planck Institute of Microstructure Physics, Weinberg 2, 06120, Halle, Germany.
² Center for Advancing Electronics Dresden (cfaed) & Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstrasse 4, 01062, Dresden, Germany.
³ School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing, Shanghai Jiao Tong University, Shanghai, 200240, P. R. China.
⁴ Dipartimento di Chimica, Materiali e Ingegneria Chimica "G. Natta", Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133, Milano, Italy.
⁵ Institute of Physical Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstraße 28/30, 48149, Münster, Germany.
⁶ Institut für Organische Chemie, Leibniz Universität Hannover, Schneiderberg 1B, 30167, Hannover, Germany.
⁷ Department of Physics & IRIS Adlershof-, Humboldt-Universität zu Berlin, 12489, Berlin, Germany.
⁸ Max Planck Institute for Polymer Research, Ackermannweg 10, 55128, Mainz, Germany.
⁹ Department of Molecular Physics, Faculty of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924, Lodz, Poland.
¹⁰ Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, 100190, P. R. China.

PMID: 37335764
DOI: 10.1002/anie.202305737

Abstract

The incorporation of nanopores into graphene nanostructures has been demonstrated as an efficient tool in tuning their band gaps and electronic structures. However, precisely embedding the uniform nanopores into graphene nanoribbons (GNRs) at the atomic level remains underdeveloped especially for in-solution synthesis due to the lack of efficient synthetic strategies. Herein we report the first case of solution-synthesized porous GNR (pGNR) with a fully conjugated backbone via the efficient Scholl reaction of tailor-made polyphenylene precursor (P1) bearing pre-installed hexagonal nanopores. The resultant pGNR features periodic subnanometer pores with a uniform diameter of 0.6 nm and an adjacent-pores-distance of 1.7 nm. To solidify our design strategy, two porous model compounds (1 a, 1 b) containing the same pore size as the shortcuts of pGNR, are successfully synthesized. The chemical structure and photophysical properties of pGNR are investigated by various spectroscopic analyses. Notably, the embedded periodic nanopores largely reduce the π-conjugation degree and alleviate the inter-ribbon π-π interactions, compared to the nonporous GNRs with similar widths, affording pGNR with a notably enlarged band gap and enhanced liquid-phase processability.

Keywords: Bandgap Engineering; Graphene Nanoribbons; In Solution; Porous; Precision Synthesis.