Molecular and Interfacial Engineering of Organic Nanosystems

Prof. Mathias Senge holds the Chair of Organic Chemistry at Trinity College Dublin, Ireland and is Hans Fischer Senior Fellow at TUM-IAS. Together with his TUM hosts Prof. Johannes Barth and Prof. Wilhelm Auwärter from the Department of Physics this Focus Group targets the molecular and interfacial engineering of organic nanosystems.

Chemistry at interfaces is very different from that in solution. This Focus Group combines classic chemical synthesis with advances in the construction of functional molecular architectures on surfaces. Our molecules of choice are porphyrins, the red and green pigments of life that give blood and green plants their characteristic colors. Recent breakthroughs in the chemistry, molecular engineering, and physical characterization of porphyrins have opened up tremendous application opportunities for functional nanodevices. We will use a molecular engineering approach, together with unique cube- and propeller-shaped linker structures, to affect a transformational advance in the molecular design and control of nanoconstructs. These systems will have tunable electronic, photonic, and chemical functionalities for the translational development of platform technologies in the materials sciences aimed at new catalysts and sensors.

Tetrapyrroles are the pigments of life and are a unique class of ubiquitous natural compounds and targets of strategic importance in biology, industry (pigments, catalysts, sensors, nanomaterials) and medicine (theranostics). Recent breakthroughs in their chemistry, molecular engineering, and physical characterization on surfaces are opening tremendous application opportunities for functional nanodevices. Thus, porphyrins will serve as innovative ‘molecular systems’ for an interdisciplinary approach towards materials science research at TUM.

The team will focus on using the unique optical, photophysical, electrochemical, and structural properties of porphyrins in conjunction with novel linker structures to affect a transformational advance in the molecular design and control of nanoconstructs with tunable electronic, photonic and chemical functionalities. The practical utility of porphyrin-based 1D, 2D, and 3D materials for device development will be assessed in collaboration with research partners from industry and academia. The key concept is the use of tetrapyrroles as ‘functional’ platforms and rigid hydrocarbon linkers (such as cubanes and bicyclopentane) as ‘structural’ systems of choice for the on-surface synthesis of nanostructured arrays. These systems will have tunable chemical and photophysical properties for the translational development of platform technologies in the materials sciences.

TUM-IAS funded postdoctoral researcher:
Dr. Biao Yang, Department of Physics, Physics of Surfaces and Interfaces

Publications by the Focus Group

2023

  • Cao, Nan; Björk, Jonas; Corral-Rascon, Eduardo; Chen, Zhi; Ruben, Mario; Senge, Mathias O.; Barth, Johannes V.; Riss, Alexander: The role of aromaticity in the cyclization and polymerization of alkyne-substituted porphyrins on Au(111). Nature Chemistry 15 (12), 2023, 1765-1772 mehr…
  • Grover, Nitika; Cheveau, Maxime; Twamley, Brendan; Kingsbury, Christopher J.; Mattern, Cornelia M.; Senge, Mathias O.: Bicyclo[1.1.1]pentane Embedded in Porphyrinoids**. Angewandte Chemie 135 (26), 2023 mehr…
  • Grover, Nitika; Cheveau, Maxime; Twamley, Brendan; Kingsbury, Christopher J.; Mattern, Cornelia M.; Senge, Mathias O.: Bicyclo[1.1.1]pentane Embedded in Porphyrinoids**. Angewandte Chemie International Edition 62 (26), 2023 mehr…
  • Osadchuk, Irina; Luts, Hanna‐Eliisa; Norvaiša, Karolis; Borovkov, Victor; Senge, Mathias O.: Supramolecular Chirogenesis in a Sterically Hindered Porphyrin: A Critical Theoretical Analysis**. Chemistry – A European Journal 29 (49), 2023 mehr…
  • Ranieri, Davide; Privitera, Alberto; Santanni, Fabio; Urbanska, Karolina; Strachan, Grant J.; Twamley, Brendan; Salvadori, Enrico; Liao, Yu‐Kai; Chiesa, Mario; Senge, Mathias O.; Totti, Federico; Sorace, Lorenzo; Sessoli, Roberta: A Heterometallic Porphyrin Dimer as a Potential Quantum Gate: Magneto‐Structural Correlations and Spin Coherence Properties. Angewandte Chemie International Edition 62 (48), 2023 mehr…
  • Yang, Biao; Niu, Kaifeng; Cao, Nan; Grover, Nitika; Zhao, Wenchao; Riss, Alexander; Björk, Jonas; Auwärter, Willi; Barth, Johannes V.; Senge, Mathias O.: On‐Surface Synthesis of Polyphenylene Wires Comprising Rigid Aliphatic Bicyclo[1.1.1]Pentane Isolator Units. Angewandte Chemie International Edition 62 (19), 2023 mehr…

2022

  • Büchner, Robby; Vaz da Cruz, Vinícius; Grover, Nitika; Charisiadis, Asterios; Fondell, Mattis; Haverkamp, Robert; Senge, Mathias O.; Föhlisch, Alexander: Fundamental electronic changes upon intersystem crossing in large aromatic photosensitizers: free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin. Physical Chemistry Chemical Physics 24 (12), 2022, 7505-7511 mehr…
  • Donohoe, Claire; Schaberle, Fábio A.; Rodrigues, Fábio M. S.; Gonçalves, Nuno P. F.; Kingsbury, Christopher J.; Pereira, Mariette M.; Senge, Mathias O.; Gomes-da-Silva, Lígia C.; Arnaut, Luis G.: Unraveling the Pivotal Role of Atropisomerism for Cellular Internalization. Journal of the American Chemical Society 144 (33), 2022, 15252-15265 mehr…
  • Gierlich, Piotr; Mucha, Sebastian G.; Robbins, Emma; Gomes‐da‐Silva, Lígia C.; Matczyszyn, Katarzyna; Senge, Mathias O.: One‐Photon and Two‐Photon Photophysical Properties of Tetrafunctionalized 5,10,15,20‐tetrakis( <i>m‐</i> hydroxyphenyl)chlorin ( <i>Temoporfin</i> ) Derivatives as Potential Two‐Photon‐Induced Photodynamic Therapy Agents. ChemPhotoChem 6 (4), 2022 mehr…
  • Ishizuka, Tomoya; Grover, Nitika; Kingsbury, Christopher J.; Kotani, Hiroaki; Senge, Mathias O.; Kojima, Takahiko: Nonplanar porphyrins: synthesis, properties, and unique functionalities. Chemical Society Reviews 51 (17), 2022, 7560-7630 mehr…
  • Kingsbury, Christopher J.; Kielmann, Marc; Twamley, Brendan; Senge, Mathias O.: Self-Organization of Porphyrin–POM Dyads: Nonplanar Diacids and Oxoanions in Low-Dimensional H-Bonding Networks. Molecules 27 (20), 2022, 7060 mehr…
  • Lewandowska-Andralojc, Anna; Gacka, Ewelina; Pedzinski, Tomasz; Burdzinski, Gotard; Lindner, Aleksandra; O’Brien, Jessica M.; Senge, Mathias O.; Siklitskaya, Aleksandra; Kubas, Adam; Marciniak, Bronislaw; Walkowiak-Kulikowska, Justyna: Understanding structure–properties relationships of porphyrin linked to graphene oxide through π–π-stacking or covalent amide bonds. Scientific Reports 12 (1), 2022 mehr…
  • Norvaiša, Karolis; O’Brien, John E.; Osadchuk, Irina; Twamley, Brendan; Borovkov, Victor; Senge, Mathias O.: Importance of molecular symmetry for enantiomeric excess recognition by NMR. Chemical Communications 58 (35), 2022, 5423-5426 mehr…
  • Teeuwen, Paula C. P.; Melissari, Zoi; Senge, Mathias O.; Williams, René M.: Metal Coordination Effects on the Photophysics of Dipyrrinato Photosensitizers. Molecules 27 (20), 2022, 6967 mehr…
  • Wiehe, Arno; Senge, Mathias O.: The Photosensitizer Temoporfin (<scp><i>m</i>THPC</scp>) – Chemical, Pre‐clinical and Clinical Developments in the Last Decade<sup>†</sup><sup>‡</sup>. Photochemistry and Photobiology 99 (2), 2022, 356-419 mehr…

2021

  • Buglak, Andrey A.; Charisiadis, Asterios; Sheehan, Aimee; Kingsbury, Christopher J.; Senge, Mathias O.; Filatov, Mikhail A.: Quantitative Structure‐Property Relationship Modelling for the Prediction of Singlet Oxygen Generation by Heavy‐Atom‐Free BODIPY Photosensitizers**. Chemistry – A European Journal 27 (38), 2021, 9934-9947 mehr…
  • Cao, Nan; Riss, Alexander; Corral-Rascon, Eduardo; Meindl, Alina; Auwärter, Willi; Senge, Mathias O.; Ebrahimi, Maryam; Barth, Johannes V.: Surface-confined formation of conjugated porphyrin-based nanostructures on Ag(111). Nanoscale 13 (47), 2021, 19884-19889 mehr…
  • Elliott, Rory; Ryan, Aoife A.; Aggarwal, Aviral; Zhu, Nianyong; Steuber, Friedrich W.; Senge, Mathias O.; Schmitt, Wolfgang: 2D Porphyrinic Metal-Organic Frameworks Featuring Rod-Shaped Secondary Building Units. Molecules 26 (10), 2021, 2955 mehr…
  • Hohlfeld, Benjamin F.; Gitter, Burkhard; Kingsbury, Christopher J.; Flanagan, Keith J.; Steen, Dorika; Wieland, Gerhard D.; Kulak, Nora; Senge, Mathias O.; Wiehe, Arno: Dipyrrinato‐Iridium(III) Complexes for Application in Photodynamic Therapy and Antimicrobial Photodynamic Inactivation. Chemistry – A European Journal 27 (21), 2021, 6440-6459 mehr…
  • Kingsbury, Christopher J.; Senge, Mathias O.: The shape of porphyrins. Coordination Chemistry Reviews 431, 2021, 213760 mehr…
  • Norvaiša, Karolis; Maguire, Sophie; Donohoe, Claire; O'Brien, John E.; Twamley, Brendan; Gomes‐da‐Silva, Ligia C.; Senge, Mathias O.: Steric Repulsion Induced Conformational Switch in Supramolecular Structures. Chemistry – A European Journal 28 (4), 2021 mehr…
  • Norvaiša, Karolis; O'Brien, John E.; Gibbons, Dáire J.; Senge, Mathias O.: Elucidating Atropisomerism in Nonplanar Porphyrins with Tunable Supramolecular Complexes. Chemistry – A European Journal 27 (1), 2021, 331-339 mehr…
  • Norvaiša, Karolis; Yeow, Kathryn; Twamley, Brendan; Roucan, Marie; Senge, Mathias O.: Strategic Synthesis of ‘Picket Fence’ Porphyrins Based on Nonplanar Macrocycles**. European Journal of Organic Chemistry 2021 (12), 2021, 1871-1882 mehr…
  • Sample, Harry C.; Emandi, Ganapathi; Twamley, Brendan; Grover, Nitika; Khurana, Bhavya; Sol, Vincent; Senge, Mathias O.: Synthesis and Properties of BODIPY Appended Tetraphenylethylene Scaffolds as Photoactive Arrays. European Journal of Organic Chemistry 2021 (29), 2021, 4136-4143 mehr…
  • Sample, Harry C.; Senge, Mathias O.: Nucleophilic Aromatic Substitution (S N Ar) and Related Reactions of Porphyrinoids: Mechanistic and Regiochemical Aspects. European Journal of Organic Chemistry 2021 (1), 2021, 7-42 mehr…

2020

  • Callaghan, Susan; Flanagan, Keith J.; O'Brien, John E.; Senge, Mathias O.: Short-Chained Anthracene Strapped Porphyrins and their Endoperoxides. European Journal of Organic Chemistry 2020 (18), 2020, 2735-2744 mehr…
  • Grover, Nitika; Emandi, Ganapathi; Twamley, Brendan; Khurana, Bhavya; Sol, Vincent; Senge, Mathias O.: Synthesis and Structure of meso ‐Substituted Dibenzihomoporphyrins. European Journal of Organic Chemistry 2020 (41), 2020, 6489-6496 mehr…
  • Grover, Nitika; Flanagan, Keith J.; Trujillo, Cristina; Kingsbury, Christopher J.; Senge, Mathias O.: An Insight into Non‐Covalent Interactions on the Bicyclo[1.1.1]pentane Scaffold. European Journal of Organic Chemistry 2021 (7), 2020, 1113-1122 mehr…
  • Grover, Nitika; Locke, Gemma M.; Flanagan, Keith J.; Beh, Michael H. R.; Thompson, Alison; Senge, Mathias O.: Bridging and Conformational Control of Porphyrin Units through Non‐Traditional Rigid Scaffolds. Chemistry – A European Journal 26 (11), 2020, 2405-2416 mehr…
  • Norvaiša, Karolis; Kielmann, Marc; Senge, Mathias O.: Porphyrins as Colorimetric and Photometric Biosensors in Modern Bioanalytical Systems. ChemBioChem 21 (13), 2020, 1793-1807 mehr…
  • Sitte, Elisabeth; Senge, Mathias O.: The Red Color of Life Transformed - Synthetic Advances and Emerging Applications of Protoporphyrin IX in Chemical Biology. European Journal of Organic Chemistry 2020 (22), 2020, 3171-3191 mehr…

2019

  • Khurana, Bhavya; Gierlich, Piotr; Meindl, Alina; Gomes-da-Silva, Lígia C.; Senge, Mathias O.: Hydrogels: soft matters in photomedicine. Photochemical & Photobiological Sciences 18 (11), 2019, 2613-2656 mehr…
  • Norvaiša, Karolis; Flanagan, Keith J.; Gibbons, Dáire; Senge, Mathias O.: Conformational Re‐engineering of Porphyrins as Receptors with Switchable N−H⋅⋅⋅X‐Type Binding Modes. Angewandte Chemie International Edition 58 (46), 2019, 16553-16557 mehr…