TY - JOUR

T1 - Bottom-up Solution Synthesis of Graphene Nanoribbons with Precisely Engineered Nanopores

AU - Niu, Wenhui

AU - Fu, Yubin

AU - Serra, Gianluca

AU - Liu, Kun

AU - Droste, Jörn

AU - Lee, Yeonju

AU - Ling, Zhitian

AU - Xu, Fugui

AU - Cojal González, José D.

AU - Lucotti, Andrea

AU - Rabe, Jürgen P.

AU - Ryan Hansen, Michael

AU - Pisula, Wojciech

AU - Blom, Paul W.M.

AU - Palma, Carlos Andres

AU - Tommasini, Matteo

AU - Mai, Yiyong

AU - Ma, Ji

AU - Feng, Xinliang

N1 - Funding Information: This research was financially supported by the National Natural Science Foundation of China (22225501 and 52203268), the EU Graphene Flagship (Graphene Core 3, 881603), H2020‐MSCA‐ITN (ULTIMATE, No. 813036), the Center for Advancing Electronics Dresden (cfaed), H2020‐EU.1.2.2.—FET Proactive Grant (LIGHT‐CAP, 101017821), the DFG‐SNSF Joint Switzerland‐German Research Project (EnhanTopo, No. 429265950), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant Nos. XDB33000000 and XDB33030300), and the DFG funded Cluster of Excellence “Matters of Activity” (No. 390648296). The authors gratefully acknowledge the GWK support for funding this project by providing computing time through the Center for Information Services and HPC (ZIH) at TU Dresden. Authors acknowledge Dortmund Electron Accelerator (DELTA) for grazing‐incidence wide‐angle x‐ray scattering (GIWAXS) measurements. Z. Ling acknowledges the China Scholarship Council NO. 202006890007. W. Pisula acknowledges the National Science Centre, Poland through the grant UMO‐2019/33/B/ST3/1550. The authors also thank Dr. Tomasz Marszalek and Yichen Jin for his experimental support and fruitful discussions. We are grateful for the assistance of Mr. Enrique Caldera for the GPC measurements, F. Drescher and Prof. E. Brunner for HR‐MS measurements, and Dr. Hartmut Komber for high‐temperature NMR measurements. Open Access funding enabled and organized by Projekt DEAL.

PY - 2023/8/23

Y1 - 2023/8/23

N2 - 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.

AB - 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.

KW - Bandgap Engineering

KW - Graphene Nanoribbons

KW - In Solution

KW - Porous

KW - Precision Synthesis

UR - http://www.scopus.com/inward/record.url?scp=85165179667&partnerID=8YFLogxK

U2 - 10.1002/anie.202305737

DO - 10.1002/anie.202305737

M3 - Article

AN - SCOPUS:85165179667

VL - 62

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 35

M1 - e202305737

ER -