Exploring the fundamentals of chemical bonding and reactivity at the atomic scale

• Applicant: Dr. Alexander Riss
• Subject Area: Physical Chemistry of Molecules, Liquids and Interfaces, Biophysical Chemistry ; Analytical Chemistry ; Experimental Condensed Matter Physics ; Solid State and Surface Chemistry, Material Synthesis
• Term: from 2020 to 2023
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 453903355

• Final Report Year: 2024

Final Report Abstract

Despite centuries of research and its fundamental role in chemistry and biology, our understanding of chemical reactivity and bonding remains incomplete. This project aimed to study these interactions at the atomic scale with unprecedented detail. Our primary strategy was to use scanning probe microscopy, particularly high-resolution atomic force microscopy (AFM), to quantify the reactivity of various chemical moieties, i.e. functional groups or atoms within different environments. A key approach involved the chemical functionalization of the AFM tip, allowing for direct measurement of the interaction potential between the probe molecule on the tip and the target molecule adsorbed on the surface. Our studies gave significant insights into the reactivity of various materials at the atomic level. Notably, we: Unraveled the influence of aromaticity and electrostatics on the reactivity of porphyrin molecules, providing valuable knowledge for designing functional molecular materials via on-surface chemistry. - Probed the chemical reactivity of the pores in nanoporous graphene, demonstrating their potential for selective molecular sieves and molecular sensors. - Quantified how the chemical environment changes the reactivity of metal centers in metal-organic networks, paving the way for the design of tailored single-atom catalysts. - Investigated π-π and metal-π interactions between organic molecules, furthering our understanding of these fundamental interactions crucial for organic synthesis and materials design. These findings not only improve our understanding of fundamental chemical interactions but also pave the way for the design and synthesis of materials with targeted properties for applications in various fields, such as solar energy conversion, molecular electronics, catalysis, sensing, and molecular nanodevices. In addition to the scientific advancements, we developed valuable tools for the research community. We created a suite of software applications and libraries specifically designed for analyzing, managing, and visualizing scanning probe microscopy data. These user-friendly, open-source apps are already gaining traction within the community, streamlining data workflows for researchers of all experience levels. The open-source nature of these tools makes these tools readily accessible for researchers, in particular also for newcomers to the field who can benefit from their intuitive interfaces and functionalities.

Publications

• Surface-confined formation of conjugated porphyrin-based nanostructures on Ag(111). Nanoscale, 13(47), 19884-19889.
  Cao, Nan; Riss, Alexander; Corral-Rascon, Eduardo; Meindl, Alina; Auwärter, Willi; Senge, Mathias O.; Ebrahimi, Maryam & Barth, Johannes V.
  
• A trade-off between ligand and strain effects optimizes the oxygen reduction activity of Pt alloys. Energy & Environmental Science, 15(12), 5181-5191.
  Kluge, Regina M.; Haid, Richard W.; Riss, Alexander; Bao, Yang; Seufert, Knud; Schmidt, Thorsten O.; Watzele, Sebastian A.; Barth, Johannes V.; Allegretti, Francesco; Auwärter, Willi; Calle-Vallejo, Federico & Bandarenka, Aliaksandr S.
  
• On-Surface Synthesis of Rigid Benzenoid- and Nonbenzenoid-Coupled Porphyrin–Graphene Nanoribbon Hybrids. The Journal of Physical Chemistry C, 126(19), 8467-8476.
  Deyerling, Joel; Pörtner, Mathias; Đorđević, Luka; Riss, Alexander; Bonifazi, Davide & Auwärter, Willi
  
• On-Surface Synthesis of Square-Type Porphyrin Tetramers with Central Antiaromatic Cyclooctatetraene Moiety. Journal of the American Chemical Society, 145(2), 967-977.
  Rascon, Eduardo Corral; Riss, Alexander; Matěj, Adam; Wiengarten, Alissa; Mutombo, Pingo; Soler, Diego; Jelinek, Pavel & Auwärter, Willi
  
• SpmImage Tycoon: Organize and analyze scanning probe microscopy data. Journal of Open Source Software, 7(77), 4644.
  Riss, Alexander
  
• On-surface synthesis of enetriynes. Nature Communications, 14(1).
  Cao, Nan; Yang, Biao; Riss, Alexander; Rosen, Johanna; Björk, Jonas & Barth, Johannes V.
  
• On‐Surface Synthesis of Polyphenylene Wires Comprising Rigid Aliphatic Bicyclo[1.1.1]Pentane Isolator Units. Angewandte Chemie, 135(19).
  Yang, Biao; Niu, Kaifeng; Cao, Nan; Grover, Nitika; Zhao, Wenchao; Riss, Alexander; Björk, Jonas; Auwärter, Willi; Barth, Johannes V. & Senge, Mathias O.
  
• The role of aromaticity in the cyclization and polymerization of alkyne-substituted porphyrins on Au(111). Nature Chemistry, 15(12), 1765-1772.
  Cao, Nan; Björk, Jonas; Corral-Rascon, Eduardo; Chen, Zhi; Ruben, Mario; Senge, Mathias O.; Barth, Johannes V. & Riss, Alexander
  
• Deceptive orbital confinement at edges and pores of carbon-based 1D and 2D nanoarchitectures. Nature Communications, 15(1).
  Piquero-Zulaica, Ignacio; Corral-Rascón, Eduardo; Diaz, de Cerio Xabier; Riss, Alexander; Yang, Biao; Garcia-Lekue, Aran; Kher-Elden, Mohammad A.; Abd, El-Fattah Zakaria M.; Nobusue, Shunpei; Kojima, Takahiro; Seufert, Knud; Sakaguchi, Hiroshi; Auwärter, Willi & Barth, Johannes V.
  
• On‐Surface Isomerization of Indigo within 1D Coordination Polymers. Angewandte Chemie, 136(15).
  Xu, Hongxiang; Chakraborty, Ritam; Adak, Abhishek Kumar; Das, Arpan; Yang, Biao; Meier, Dennis; Riss, Alexander; Reichert, Joachim; Narasimhan, Shobhana; Barth, Johannes V. & Papageorgiou, Anthoula C.