Planar and Bowl-shaped Electron-poor Polycyclic Aromatic Hydrocarbons

• Applicant: Professor Dr. Frank Würthner
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2017 to 2024
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 377001809

• Final Report Year: 2024

Final Report Abstract

In this project a convergent synthetic route was developed for imide-functionalized polycyclic aromatic hydrocarbons (PAHs) whose applications were subsequently studied in various fields. The first phase focused on optimizing a [3+3] annulation reaction for synthesizing imidesubstituted PAHs, overcoming challenges such as expanding substrate scope and accommodating bulky N-substituents. Successful synthesis of diverse planar and bowl-shaped nanographenes including the first carbon nanocone, was achieved. In the second phase, the project expanded to include the formation of donor–acceptor complexes, multilayer PAHs, and a new multi-imide nanographene molecule with a hole in its interior. These supramolecular entities hold potential for applications in materials science, organic electronics, and optoelectronics. Thus, the synthesized PAHs demonstrated promising properties for organic semiconductor applications, with high absorption coefficients, stability, and suitable energy levels for efficient charge transport. Notably, several imide-containing PAHs showed potential as electron acceptor materials in organic solar cells, achieving high power conversion efficiencies for the conversion of sunlight into electricity. The new nanographene with a hole (“benzene defect”) was applied to study halide anion binding and passage of halide anions through the hole.

Publications

• Electron-Poor Bowl-Shaped Polycyclic Aromatic Dicarboximides: Synthesis, Crystal Structures, and Optical and Redox Properties. Organic Letters, 19(19), 5328-5331.
  Shoyama, Kazutaka; Schmidt, David; Mahl, Magnus & Würthner, Frank
  
• A General Synthetic Route to Polycyclic Aromatic Dicarboximides by Palladium-Catalyzed Annulation Reaction. The Journal of Organic Chemistry, 83(10), 5339-5346.
  Shoyama, Kazutaka; Mahl, Magnus; Seifert, Sabine & Würthner, Frank
  
• Tetrachlorinated Polycyclic Aromatic Dicarboximides: New Electron‐Poor π‐Scaffolds and NIR Emitters by Palladium‐Catalyzed Annulation Reaction. Chemistry – A European Journal, 24(37), 9409-9416.
  Mahl, Magnus; Shoyama, Kazutaka; Rühe, Jessica; Grande, Vincenzo & Würthner, Frank
  
• Palladium-Catalyzed [3+2] Annulation of Naphthalimide Acceptors and Thiophene Donors. The Journal of Organic Chemistry, 85(1), 142-149.
  Shoyama, Kazutaka; Mahl, Magnus; Niyas, M. A.; Ebert, Markus; Kachler, Valentin; Keck, Christoph & Würthner, Frank
  
• Self‐Assembly of Bowl‐Shaped Naphthalimide‐Annulated Corannulene. ChemistryOpen, 9(1), 32-39.
  Renner, Rebecca; Stolte, Matthias & Würthner, Frank
  
• Synthesis of a Carbon Nanocone by Cascade Annulation. Journal of the American Chemical Society, 141(33), 13008-13012.
  Shoyama, Kazutaka & Würthner, Frank
  
• Base‐Assisted Imidization: A Synthetic Method for the Introduction of Bulky Imide Substituents to Control Packing and Optical Properties of Naphthalene and Perylene Imides. Angewandte Chemie International Edition, 59(32), 13401-13405.
  Mahl, Magnus; Shoyama, Kazutaka; Krause, Ana‐Maria; Schmidt, David & Würthner, Frank
  
• Bowl-Shaped Naphthalimide-Annulated Corannulene as Nonfullerene Acceptor in Organic Solar Cells. Organic Materials, 02(03), 229-234.
  Menekse, Kaan; Renner, Rebecca; Mahlmeister, Bernhard; Stolte, Matthias & Würthner, Frank
  
• NIR‐Absorbing π‐Extended Azulene: Non‐Alternant Isomer of Terrylene Bisimide. Angewandte Chemie International Edition, 59(37), 15908-15912.
  Pigulski, Bartłomiej; Shoyama, Kazutaka & Würthner, Frank
  
• Synthesis of polycyclic aromatic hydrocarbons by palladium-catalysed [3 + 3] annulation. Organic Chemistry Frontiers, 7(19), 2925-2930.
  Pigulski, Bartłomiej; Ximenis, Marta; Shoyama, Kazutaka & Würthner, Frank
  
• Fluorescence Enhancement by Supramolecular Sequestration of a C54-Nanographene Trisimide by Hexabenzocoronene. Journal of the American Chemical Society, 144(13), 5718-5722.
  Pigulski, Bartłomiej; Shoyama, Kazutaka; Sun, Meng-Jia & Würthner, Frank
  
• Multilayer stacks of polycyclic aromatic hydrocarbons. Nature Chemistry, 14(4), 457-462.
  Mahl, Magnus; Niyas, M. A.; Shoyama, Kazutaka & Würthner, Frank
  
• Supramolecularly Engineered Bulk‐Heterojunction Solar Cells with Self‐Assembled Non‐Fullerene Nanographene Tetraimide Acceptors. Solar RRL, 7(2).
  Menekse, Kaan; Mahl, Magnus; Albert, Julius; Niyas, M. A.; Shoyama, Kazutaka; Stolte, Matthias & Würthner, Frank
  
• C64 Nanographene Tetraimide—A Receptor for Phthalocyanines with Subnanomolar Affinity. Angewandte Chemie International Edition, 62(25).
  Niyas, M. A.; Shoyama, Kazutaka & Würthner, Frank
  
• Naphthalimide-Annulated [n]Helicenes: Red Circularly Polarized Light Emitters. Journal of the American Chemical Society, 145(17), 9886-9894.
  Tian, Xiaoqi; Shoyama, Kazutaka; Mahlmeister, Bernhard; Brust, Felix; Stolte, Matthias & Würthner, Frank
  
• Naphthalimide-Fused Subphthalocyanines: Electron-Deficient Materials Prepared by Cascade Annulation. ACS Materials Letters, 5(2), 543-548.
  Labella, Jorge; Shoyama, Kazutaka; Guzmán, David; Schembri, Tim; Stolte, Matthias; Torres, Tomás & Würthner, Frank
  
• Nitrogen-doped polycyclic aromatic hydrocarbons by a one-pot Suzuki coupling/intramolecular SNAr reaction. Chemical Science, 14(2), 284-290.
  Tian, Xiaoqi; Shoyama, Kazutaka & Würthner, Frank
  
• Room‐Temperature Near‐Infrared Phosphorescence from C64 Nanographene Tetraimide by π‐Stacking Complexation with Platinum Porphyrin. Angewandte Chemie International Edition, 63(33).
  Niyas, M. A.; Garain, Swadhin; Shoyama, Kazutaka & Würthner, Frank
  
• Ternary π–π Stacking Complexes by Allosteric Regulation in Multilayer Nanographenes. Journal of the American Chemical Society, 146(43), 29728-29734.
  Niyas, M. A.; Shoyama, Kazutaka & Würthner, Frank
  
• Bilayer nanographene reveals halide permeation through a benzene hole. Nature, 637(8047), 854-859.
  Niyas, M. A.; Shoyama, Kazutaka; Grüne, Matthias & Würthner, Frank
  
• Convergent synthetic approaches to polycyclic aromatic dicarboximides. Organic Chemistry Frontiers, 12(1), 328-345.
  Shoyama, Kazutaka & Würthner, Frank