pi-Expanded Cyanocarbons: A New Class of Versatile Electron Acceptors

• Applicant: Professor Dr. Milan Kivala
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2018 to 2023
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 401247651

• Final Report Year: 2024

Final Report Abstract

The project focused on the synthesis and study of cyano-rich π-conjugated compounds, socalled cyanocarbons, as exceptionally strong electron acceptors with unique optoelectronic and redox properties and reactivity. The multiple strongly polarized cyano groups were expected to significantly alter the supramolecular behavior of the compounds both in the solid state and on surfaces. Next to the synthetic challenges, the highly exploratory project aimed to investigate the impact of cyanation on the fundamental characteristics of the compounds with the goal of developing a new class of electron deficient functional materials.

Publications

• Edge Phonon Excitations in a Chiral Self-Assembled Supramolecular Nanoribbon. The Journal of Physical Chemistry Letters, 10(19), 5830-5835.
  Cojal, González José D.; Li, Juan; Stöhr, Meike; Kivala, Milan; Palma, Carlos-Andres & Rabe, Jürgen P.
  
• Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States. Small, 15(33).
  Müller, Kathrin; Schmidt, Nico; Link, Stefan; Riedel, René; Bock, Julian; Malone, Walter; Lasri, Karima; Kara, Abdelkader; Starke, Ulrich; Kivala, Milan & Stöhr, Meike
  
• Isomeric Dithienophosphepines: The Impact of Ring Fusion on Electronic and Structural Properties. Chemistry – A European Journal, 26(16), 3474-3478.
  Padberg, Kevin; Ascherl, Johannes D. R.; Hampel, Frank & Kivala, Milan
  
• Metalated Graphyne-Based Networks as Two-Dimensional Materials: Crystallization, Topological Defects, Delocalized Electronic States, and Site-Specific Doping. ACS Nano, 14(12), 16887-16896.
  Yang, Zechao; Sander, Tim; Gebhardt, Julian; Schaub, Tobias A.; Schönamsgruber, Jörg; Soni, Himadri R.; Görling, Andreas; Kivala, Milan & Maier, Sabine
  
• On‐Surface Assembly of Hydrogen‐ and Halogen‐Bonded Supramolecular Graphyne‐Like Networks. Angewandte Chemie International Edition, 59(24), 9549-9555.
  Yang, Zechao; Fromm, Lukas; Sander, Tim; Gebhardt, Julian; Schaub, Tobias A.; Görling, Andreas; Kivala, Milan & Maier, Sabine
  
• Phosphorus‐Containing Dibenzonaphthanthrenes: Electronic Fine Tuning of Polycyclic Aromatic Hydrocarbons through Organophosphorus Chemistry. Chemistry – A European Journal, 26(58), 13157-13162.
  Ascherl, Johannes D. R.; Neiß, Christian; Vogel, Alexander; Graf, Jürgen; Rominger, Frank; Oeser, Thomas; Hampel, Frank; Görling, Andreas & Kivala, Milan
  
• Fully Bridged Triphenylamines Comprising Five‐ and Seven‐Membered Rings. Chemistry – A European Journal, 28(34).
  Michalsky, Ina; Gensch, Viktoria; Walla, Christian; Hoffmann, Marvin; Rominger, Frank; Oeser, Thomas; Tegeder, Petra; Dreuw, Andreas & Kivala, Milan
  
• Control of Photoinduced Charge Transfer Through Selective Cyanation of Spirofluorene‐Bridged N‐Heterotriangulenes. Advanced Optical Materials, 12(27).
  Jocic, Angelina; Galindo, Danyellen; Weidlich, Anna; Zerhoch, Jonathan; Rominger, Frank; Buckup, Tiago; Deschler, Felix; Dreuw, Andreas & Kivala, Milan
  
• Electronic Properties of Interfaces between N-Heterotriangulene Donors and Strong Tetracyanoquinodimethane Acceptors. The Journal of Physical Chemistry C, 128(34), 14399-14406.
  Ajdari, Mohsen; Pappenberger, Ronja; Walla, Christian; Michalsky, Ina; Maaß, Friedrich; Kivala, Milan; Dreuw, Andreas & Tegeder, Petra
  
• Octacyano-substituted tridecacyclene: a non-benzenoid cyanocarbon with low-lying LUMO and multistage redox properties. Chemical Communications, 61(31), 5754-5757.
  Misselwitz, Erik; Spengler, Jonas; Rominger, Frank & Kivala, Milan