FY2021 Annual Report

Organic and Carbon Nanomaterials Unit
Assistant Professor Akimitsu Narita

Abstract

FY2021 was the fourth year of the unit, and the second year of operation physically at OIST after the opening of Lab4 in 2020. The unit has welcomed Dr. Hiroki Hanayama (JSPS Postdoctoral Fellow) as well as Dr. Hao Zhao (Postdoctoral Scholar) and Dr. Jingyun Tan (Postdoctoral Scholar), who could finally relocate to OIST. Mr. Saurav Raj (Special Research Student) has successfully defended his Master thesis at his home institution and started his PhD studies at OIST. We have hosted four OIST rotation students and a visiting research student. We have mainly worked on the synthesis of functionalized nanographene molecules for optoelectronic and bioimaging applications as well as exploration of novel nanographenes with helical structures. We have also joined a new JSPS KAKENHI project (Fostering Joint International Research (B); 21KK0091) as a co-investigator and continued to work on the JSPS KAKENHI project No. 19K24686 and the EU project "LIGHT-CAP" as an extra-EU partner.

1. Staff

  • Dr. Zakaria Ziadi, Staff Scientist 
  • Dr. Xiushang Xu, Postdoctoral Scholar
  • Dr. Goudappagouda, Postdoctoral Scholar
  • Dr. Jingyun Tan, Postdoctoral Scholar
  • Dr. Hao Zhao, Postdoctoral Scholar
  • Dr. Hiroki Hanayama, Research Fellow (JSPS Postdoctoral Fellow)
  • Mr. Saurav Raj, Special Research Student (-Dec.2021),  OIST Rotation Student (Jan.2022-Apr.2022)
  • Mr. Rengo Yoshioka, OIST Rotation Student (Sep.2021-Dec.2021)
  • Ms. Samira Gmuer, OIST Rotation Student (Sep.2021-Dec.2021)
  • Mr. Takatsugu Onishi, OIST Rotation Student (Jan.2022-Apr.2022)
  • Ms. Mi Yan, Visiting Research Student
  • Ms. Ayumi Shimojima, Research Unit Administrator

2. Collaborations

2.1 Synthesis and Characterizations of Functional Polycyclic Aromatic Hydrocarbons (PAHs) and Atomically Precise Graphene Nanoribbons (GNRs)

  • Type of collaboration: Joint research
  • Researchers:
    • Prof. Klaus Müllen, Max Planck Institute for Polymer Research (MPIP), Mainz, Germany
    • Prof. Roman Fasel, nanotech@surfaces laboratory, Empa – Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, Switzerland
    • Prof. Xinliang Feng, Faculty of Chemistry and Food Chemistry and Center for Advancing Electronics Dresden, Technical University of Dresden, Germany
    • Prof. Yunbin Hu, College of Chemistry and Chemical Engineering, Central South University, Changsha, China
    • Dr. Marco Di Giovannantonio, Consiglio Nazionale delle Ricerche (CNR), Istituto di Struttura della Materia (ISM), Roma, Italy

2.2 Investigations of Nanographene-Based Fluorophores for the Super-Resolution Imaging

  • Type of collaboration: Joint research
  • Researchers:
    • Prof. Mischa Bonn, MPIP, Mainz, Germany
    • Dr. Xiaomin Liu, MPIP, Mainz, Germany

2.3 Investigations of Photophysical Properties of Novel PAHs and Their Functionalized Derivatives and Their Integration into Lasing Devices

  • Type of collaboration: Joint research
  • Researchers:
    • Prof. Guglielmo Lanzani, Center for Nano Science and Technology, Istituto Italiano di Tecnologia (IIT), Milano, Italy; Physics Department, Politecnico di Milano, Italy
    • Prof. Francesco Scotognella, Physics Department, Politecnico di Milano, Italy
    • Dr. Giuseppe M. Paternò, Physics Department, Politecnico di Milano, Italy
    • Prof. María A. Díaz-García, Departamento de Física Aplicada and Instituto Universitario de Materiales de Alicante, Universidad de Alicante, Spain

2.4 Investigations of Photophysical and Electrochemical Properties of PAHs and Their Dimers as Novel π-Extended Biaryls

  • Type of collaboration: Joint research
  • Researchers:
    • Prof. Andrew Musser, Department of Chemistry & Chemical Biology, Cornell University, Ithaca, NY, USA
    • Prof. Massimo Marcaccio, Dipartimento di Chimica "Giacomo Ciamician", Università di Bologna, Italy

2.5 Fabrication and Device Applications of Graphene-Nanographene van der Waals Heterostructures and Investigation of Interlayer Charge-Transfer/Exfoliation and Photoconductivity Studies of Solution-Synthesized GNRs and Other Nanocarbon Materials

  • Type of collaboration: Joint research
  • Researchers:
    • Prof. Paolo Samorì, University of Strasbourg, CNRS, ISIS UMR 7006, Strasbourg, France
    • Prof. Mischa Bonn, MPIP, Mainz, Germany
    • Dr. Hai Wang, MPIP, Mainz, Germany 

2.6 Investigations of Photoluminescence Properties of Novel PAHs and GNRs 

  • Type of collaboration: Joint research
  • Researchers:
    • Prof. Jean-Sébastien Lauret, Ecole Normale Supérieure de Paris Saclay, Orsay cedex, France
    • Dr. Stéphane Campidelli, CEA-Saclay, Gif sur Yvette, France

3. Activities and Findings

3.1 Synthesis and Characterizations of Atomically Precise Graphene Quantum Dots (GQDs) and Their Functionalization toward Photonic Applications

Large polycyclic aromatic hydrocarbons (PAHs) have chemical structures of nanoscale graphene fragments, or so-called graphene quantum dots (GQDs), and show unique structure-dependent properties promising for optoelectronic and photonic applications. We have continued to work on the functionalization of dibenzo[hi,st]ovalene (DBOV), which can be regarded as a GQD or “nanographene” with a combination of zigzag- and armchair-type edge structures (cf. review articles 1 and 2 in 4.1.2 below). DBOV derivatives have demonstrated very high stability, strong red fluorescence, stimulated emission, and environment-free blinking behavior, which rendered them highly interesting for lasing and super-resolution imaging applications. We have worked on the synthesis of a variety of novel functionalized DBOV derivatives with electron-donating or -withdrawing groups and/or hydrophilic substituents for the solubilization in water towards bioimaging and other biomedical applications. For example, water-soluble DBOVs with linkers for the bioconjugation were synthesized and their applications as the blinking fluorophore for the super-solution bioimaging by the single-molecule localization microscope (SMLM) were explored through Collaboration 2.2. Acid- and metal-ion-induced, reversible quenching of fluorescence and blinking behavior of a nitrogen-doped, diaza-DBOV was also demonstrated through this collaboration, enabling pH-sensitive super-resolution imaging (publication 10 in 4.1.1). On the other hand, the detailed investigation of photophysical processes, in particular the stimulated emission, of the DBOV derivatives and fabrication of lasing devices were performed through Collaboration 2.3 (publication 7 in 4.1.1). Moreover, by utilizing the high-resolution transmission electron microscope (HR-TEM) at the Imaging Section of OIST, we have elucidated the nanoscale layer structure of DBOV-based two-dimensional covalent organic framework (2D DBOV-COF) prepared at MPIP, providing the key characterization result to reveal the unique ABC-type stacking, supporting the power X-ray diffraction data (publication 5 in 4.1.1). Apart from DBOVs, we have explored the synthesis of novel PAHs, such as those with a combination of zigzag and fjord edges or extended helical structures. We have also explored covalently bonded dimers of PAHs as novel π-extended biaryls, and for example synthesized a derivative of 5,5'-bibenzo[rst]pentaphene (BBPP) and elucidated its axial chirality and chiroptical properties (publication 3 in 4.1.1). Furthermore, photophysical and electrochemical properties of BBPP were carefully studied through Collaboration 2.4, demonstrating symmetry-breaking charge transfer as well as intense electrochemiluminescence (ECL). 

3.2 On-Surface Synthesis of GQDs and Graphene Nanoribbons 

On-surface synthesis under the ultrahigh vacuum allows for the synthesis of atomically precise carbon nanostructures, including quasi-zero-dimensional GQDs and quasi-one-dimensional graphene nanoribbons (GNRs), and their direct visualization by atomic-resolution scanning probe microscope. We continued to work on the cooperative projects of Collaboration 2.1 (publications 9, 11, and 12 in 4.1.1; cf. annual report of FY2020), and focused on the synthesis of new molecular precursors toward fabrication of GQDs and GNRs with exotic electronic states. 

3.3 Water-Soluble Polymer Nanoparticles Containing Functional PAHs 

The atomically precise GQDs and other functional PAHs are highly hydrophobic and typically insoluble in water, which hinders their bioimaging and other biomedical applications. Water-soluble GQDs can be obtained by installing hydrophilic substituents at the peripheral positions, but it requires additional synthetic steps and often tedious purification processes. To circumvent this problem, we have explored the encapsulation of double [7]helicene (D7H) as a hydrophobic PAH in amphiphilic polymers, and successfully obtained polymer nanoparticles containing D7H (D7H-NPs), which were well dispersed in water(publication 6 in 4.1.1). The D7H-NPs in water displayed UV-vis absorption and fluorescence spectra virtually identical to those of D7H in organic solvents, and could be used as fluorophores for bioimaging. Moreover, the D7H-NPs demonstrated efficient generation of both singlet oxygen and superoxide anion upon while light irradiation and could kill the 4T1 cancer cells, showing the potential as the phototherapeutic agent.

4. Publications

4.1 Journals

4.1.1 Original Research Articles
  1. A. Götz, X.-Y. Wang, A. Ruini, W. Zheng, P. Soltani, R. Graf, A. Tries, J. Li, C.-A. Palma, E. Molinari, M. R. Hansen, H. I. Wang,* D. Prezzi,* K. Müllen,* A. Narita,* Band structure modulation by methoxy-functionalization of graphene nanoribbons. J. Mater. Chem. C 2022, Advance Article, DOI: 10.1039/D1031TC05695F. (Themed collection: Journal of Materials Chemistry C HOT Papers)
  2. X. Yu, S. Fu, M. Mandal, X. Yao, Z. Liu, W. Zheng, P. Samorì, A. Narita, K. Müllen, D. Andrienko, M. Bonn, H. I. Wang, Tuning interfacial charge transfer in atomically precise nanographene–graphene heterostructures by engineering van der Waals interactions. J. Chem. Phys. 2022, 156, 074702.
  3. X. Xu, S. Gunasekaran, S. Renken, L. Ripani, D. Schollmeyer, W. Kim, M. Marcaccio, A. Musser,* A. Narita,* Synthesis and Characterizations of 5,5′-Bibenzo[rst]pentaphene with Axial Chirality and Symmetry-Breaking Charge Transfer. Adv. Sci. 2022, 9, 2200004. (Special Issue: Functional Carbon-Rich Materials — Anniversary Issue for Klaus Müllen)
  4. Z. Liu, Y. Hu, W. Zheng, C. Wang, W. Baaziz, F. Richard, O. Ersen, M. Bonn, H. I. Wang, A. Narita, A. Ciesielski, K. Müllen, P. Samorì, Untying the Bundles of Solution-Synthesized Graphene Nanoribbons for Highly Capacitive Micro-Supercapacitors. Adv. Funct. Mater. 2022, Early View, 2109543.
  5. E. Jin, S. Fu, H. Hanayama, M. A. Addicoat, W. Wei, Q. Chen, R. Graf, K. Landfester, M. Bonn, K. A. I. Zhang,* H. I. Wang,* K. Müllen,* A. Narita,* A Nanographene-Based Two-Dimensional Covalent Organic Framework as a Stable and Efficient Photocatalyst. Angew. Chem. Int. Ed. 2022, 61, e202114059.
  6. H. Zhao, X. Xu, L. Zhou, Y. Hu, Y. Huang, A. Narita,* Water-Soluble Nanoparticles with Twisted Double [7]Carbohelicene for Lysosome-Targeted Cancer Photodynamic Therapy. Small 2022, 18, 2105365 (Invited contribution to Rising Stars series).
  7. G. M. Paternò, Q. Chen, R. Muñoz-Mármol, M. Guizzardi, V. Bonal, R. Kabe, A. J. Barker, P. G. Boj, S. Chatterjee, Y. Ie, J. M. Villalvilla, J. A. Quintana, F. Scotognella, K. Müllen, M. A. Díaz-García,* A. Narita,* G. Lanzani,* Excited states engineering enables efficient near-infrared lasing in nanographenes. Mater. Horiz. 2022, 9, 393–404.
  8. Z. Liu, H. Qiu, S. Fu, C. Wang, X. Yao, A. G. Dixon, S. Campidelli, E. Pavlica, G. Bratina, S. Zhao, L. Rondin, J.-S. Lauret, A. Narita, M. Bonn, K. Müllen, A. Ciesielski, H. I. Wang, P. Samorì, Solution-Processed Graphene–Nanographene van der Waals Heterostructures for Photodetectors with Efficient and Ultralong Charge Separation. J. Am. Chem. Soc. 2021, 143, 17109–17116.
  9. Q. Sun, Y. Yan, X. Yao, K. Müllen, A. Narita, R. Fasel, P. Ruffieux, Evolution of the Topological Energy Band in Graphene Nanoribbons. J. Phys. Chem. Lett. 2021, 12, 8679–8684.
  10. E. Jin, Q. Yang, C.-W. Ju, Q. Chen, K. Landfester, M. Bonn,* K. Müllen,* X. Liu,* A. Narita,* A Highly Luminescent Nitrogen-Doped Nanographene as an Acid- and Metal-Sensitive Fluorophore for Optical Imaging. J. Am. Chem. Soc. 2021, 143, 10403–10412. (Highlighted in Synfacts 2021, 17, 1093.)
  11. S. Mishra, X. Yao, Q. Chen, K. Eimre, O. Gröning, R. Ortiz, M. D. Giovannantonio, J. C. Sancho-García, J. Fernández-Rossier, C. A. Pignedoli, K. Müllen, P. Ruffieux, A. Narita,* R. Fasel,* Giant magnetic exchange coupling in rhombus-shaped nanographenes with zigzag periphery. Nature Chem. 2021, 13, 581–586.
  12. X. Xu, M. Di Giovannantonio, J. I. Urgel, C. A. Pignedoli, P. Ruffieux, K. Müllen,* R. Fasel,* A. Narita,* On-surface activation of benzylic C-H bonds for the synthesis of pentagon-fused graphene nanoribbons. Nano Res. 2021, 14, 4754–4759.
  13. G. Zhang, J. Tan, L. Zhou, C. Liu, J. Liu, Y. Zou, A. Narita, Y. Hu, S-Shaped Double Helicene Diimides: Synthesis, Self-Assembly, and Mechanofluorochromism. Org. Lett. 2021, 23, 6183–6188. (Selected as the Cover)
  14. J. Weippert, P. Huber, J. Hauns, A. Narita, K. Müllen, K. Y. Amsharov, A. Böttcher, M. M. Kappes, Comparative Study of Direct and Graphite-Mediated Oxidation of Large PAHs. J. Phys. Chem. C 2021, 125, 8163–8176.
  15. X. Yao, W. Zheng, S. Osella, Z. Qiu, S. Fu, D. Schollmeyer, B. Müller, D. Beljonne, M. Bonn, H. I. Wang, K. Müllen,* A. Narita,* Synthesis of Nonplanar Graphene Nanoribbon with Fjord Edges. J. Am. Chem. Soc. 2021, 143, 5654–5658.
4.1.2 Review Article
  1. Z. Liu, S. Fu, X. Liu, A. Narita, P. Samorì, M. Bonn, H. I. Wang, Small Size, Big Impact: Recent Progress in Bottom-Up Synthesized Nanographenes for Optoelectronic and Energy Applications. Adv. Sci. 2022, 9, 2106055. (Special Issue: Functional Carbon-Rich Materials — Anniversary Issue for Klaus Müllen)
  2. G. M. Paternò,* Goudappagouda, Q. Chen, G. Lanzani, F. Scotognella, A. Narita,* Large Polycyclic Aromatic Hydrocarbons as Graphene Quantum Dots: from Synthesis to Spectroscopy and Photonics. Adv. Optical Mater. 2021, 9, 2100508. (Selected as the Inside Front Cover; Special Issue: Optical Properties and Applications of Crystalline Materials)
4.1.3 Articles without peer-review
  1. 成田明光, ナノグラフェンのボトムアップ合成と多彩な物性, 化学と工業, 2021, 74, 406–408.

4.2 Books and other one-time publications

Nothing to report

4.3 Oral and Poster Presentations

Invited Talks at Conferences and Symposiums
  1. Narita, A. 低次元炭素材料のボトムアップ合成と多彩な物性, 基調講演, 第５８回炭素材料夏季セミナー (online), Gunma University, Gunma, Japan, May 27, 2021.
  2. Narita, A. グラフェン量子ドットやグラフェンナノリボンのボトムアップ精密合成と物性評価 (Bottom-up Synthesis and Characterizations of Graphene Nanoribbons and Graphene Quantum Dots), 第82回応用物理学会秋季学術講演会 (The 82nd Japan Society of Applied Physics (JSAP) Autumn Meeting 2021, online), Aoyama Gakuen University, Tokyo, Japan, September 11, 2021
  3. Narita, A. 表面で焼き上げたパイはいかが？, 日本化学会秋季事業 第11回CSJ化学フェスタ2021 (11st CSJ Chemistry Festa, online), Japan, October 21, 2021.
  4. Narita, A. Bottom-up synthesis of atomically precise graphene nanostructures under visualization by high-resolution scanning probe microscopy, Pacifichem 2021 (online), December 16–21, 2021.
  5. Narita, A. Synthetic Exploration of Precision Graphene Nanostructures and Emerging Photonic Applications, Virtual Workshop Advanced Precision Carbon Nanostructures (online), January 21, 2022.
  6. Narita, A. Bottom-up Synthesis and Functionalization of Graphene Quantum Dots with Atomically Precise Structures, nanoGe Spring Meeting 2022 (online), March 7–11, 2022.
  7. Narita, A. 局在スピンを有するグラフェンナノリボンの精密合成 (Precision Synthesis of Graphene Nanoribbons with Localized Spins), 日本化学会第102回春季年会 (2022) (The 102nd Chemical Society of Japan Annual Meeting, online), Japan, March 23–26, 2022.
Poster presentations
  1. Ripania, L.; Marcaccioa, M.; Xu, X.; Narita, A. Redox behaviour of dibenzopyrene derivatives and their electrochemical generation of conductive film, SCI2021 XXVII National Congress of the Italian Chemical Society, Italy, September 14–23, 2021

5. Intellectual Property Rights and Other Specific Achievements

Nothing to report

6. Meetings and Events

Nothing to report

7. Other

7.1 Grants and Fellowships

  • Akimitsu Narita (PI), JSPS KAKENHI, Fund for the Promotion of Joint International Research (Home-Returning Researcher Development Research), らせん構造を有するナノグラフェンおよびグラフェンナノソレノイドの合成と物性評価, 19K24686, FY2020-FY2022
  • Akimitsu Narita (Co-Investigator), JSPS KAKENHI, Fund for the Promotion of Joint International Research (Fostering Joint International Research (B)), 先端分光計測と精密合成を活用したグラフェンナノリボンの微細構造と機能の制御, 21KK0091, FY2021-FY2024
  • Hiroki Hanayama, JSPS Research Fellowship for Young Scientist (PD) and Grant-in-Aid for JSPS Fellows, 透過電子顕微鏡構造解析を鍵とするグラフェンナノリボンの面修飾反応の開発とその応用, 21J01147, FY2021-FY2023

7.2 Other Projects

  • Participation as an extra-EU partner in the FET Proactive project LIGHT-CAP: Multi-electron processes for light driven electrodes and electrolytes in conversion and storage of solar energy, the European Consortium funded by the European Union’s Horizon 2020 research and innovation programme under grant agreement No. 101017821, 2021-2024