Article
Chemistry, Multidisciplinary
Mowpriya Das, Conor Hogan, Robert Zielinski, Milan Kubicki, Maximilian Koy, Canan Kosbab, Simone Brozzesi, Ankita Das, Mike Thomas Nehring, Viktoria Balfanz, Juls Bruehne, Mario Daehne, Martin Franz, Norbert Esser, Frank Glorius
Summary: In this study, we investigated the adsorption properties of N-heterocyclic olefins (NHOs) on silicon and found that the adsorption geometry strongly depends on the N-substituents. Different N-substituents result in different adsorption geometries, with larger N-substituents favoring upright adsorption and smaller N-substituents favoring flat-lying geometry. These different geometries have a significant impact on the properties of the obtained monolayers, such as their work function.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Peter Knecht, Dennis Meier, Joachim Reichert, David A. Duncan, Martin Schwarz, Johannes T. Kuechle, Tien-Lin Lee, Peter S. Deimel, Peter Feulner, Francesco Allegretti, Willi Auwaerter, Guillaume Medard, Ari Paavo Seitsonen, Johannes Barth, Anthoula C. Papageorgiou
Summary: Ru-porphyrins serve as pedestals for the assembly of N-heterocyclic carbenes (NHCs) on solid surfaces. A phenomenon of transferring Ru-porphyrin molecules from the surface to the next layer can be observed upon deposition of a simple NHC ligand on a close-packed Ru-porphyrin monolayer. The uptake of NHC induces a rearrangement of the molecular layer, which can be reversed by thermal desorption of the NHC ligand. Understanding such mass transport processes is crucial for surface functionalization with carbenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Iris Berg, Luca Schio, Justus Reitz, Elena Molteni, Linoy Lahav, Carolina Gutierrez Bolanos, Andrea Goldoni, Cesare Grazioli, Guido Fratesi, Max M. Hansmann, Luca Floreano, Elad Gross
Summary: In this study, the self-assembly of N-heterocyclic olefins (NHOs) on gold surface was investigated using experimental and computational methods. It was found that NHOs can self-assemble into dimers, trimers, and tetramers, forming stable monolayers. The study also revealed that NHOs can adsorb on gold surface in a flat-lying geometry through coordination with gold adatoms, and the surface interaction can be further increased by functionalizing the backbone with methyl groups, leading to enhanced thermal stability and impact on work-function values.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Daniel J. Rizzo, Sara Shabani, Bjarke S. Jessen, Jin Zhang, Alexander S. McLeod, Carmen Rubio-Verdu, Francesco L. Ruta, Matthew Cothrine, Jiaqiang Yan, David G. Mandrus, Stephen E. Nagler, Angel Rubio, James C. Hone, Cory R. Dean, Abhay N. Pasupathy, D. N. Basov
Summary: The researchers successfully created nanometer-scale lateral p-n junctions using graphene/alpha-RuCl3 heterostructure near graphene nanobubbles. Through STM/STS and s-SNOM techniques, they investigated the electronic and optical responses of nanobubble p-n junctions, achieving p-n junctions with a width of around 3 nm and an electric field of approximately 10(8) V/m. The study also utilized ab initio density functional theory calculations to corroborate experimental data and provide insights into charge transfer mechanisms in 2D materials.
Article
Chemistry, Multidisciplinary
Juan J. Navarro, Mowpriya Das, Sergio Tosoni, Felix Landwehr, Maximilian Koy, Markus Heyde, Gianfranco Pacchioni, Frank Glorius, Beatriz Roldan Cuenya
Summary: N-Heterocyclic carbenes (NHCs) show superior properties in self-assembled monolayers (SAMs) and understanding the influence of the substrate on the molecular arrangement is crucial. This study reveals that on Cu(100), NHCs form mostly disordered phases, while on Cu(111), well-defined structures ranging from magic-number islands to molecular ribbons are observed. Diffusion and commensurability play a key role in determining the observed arrangements, providing insights into molecule-substrate interaction and the potential for tuning nanopatterned structures based on NHC assemblies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Peng Fan, Hui Chen, Xingtai Zhou, Lu Cao, Geng Li, Meng Li, Guojian Qian, Yuqing Xing, Chengmin Shen, Xiancheng Wang, Changqing Jin, Genda Gu, Hong Ding, Hong-Jun Gao
Summary: We demonstrate the manipulation of Abrikosov vortices on the surfaces of Fe(Te,Se) and LiFeAs by utilizing one-dimensional wrinkles and low-temperature scanning tunneling microscopy/spectroscopy (STM/S). The wrinkles trap the Abrikosov vortices induced by the external magnetic field, and we are able to tailor and manipulate the wrinkles using an STM tip. Surprisingly, we show that the pinned vortices move together with these wrinkles even at high magnetic field up to 6 T. This work provides a universal and effective method for manipulating wrinkle-pinned vortices and simultaneously measuring the local density of states on the surfaces of iron-based superconductors.
Article
Chemistry, Multidisciplinary
Caleb Z. Zerger, Linsey K. Rodenbach, Yi-Ting Chen, Benjamin Safvati, Morgan Z. Brubaker, Steven Tran, Tse-An Chen, Ming-Yang Li, Lain-Jong Li, David Goldhaber-Gordon, Hari C. Manoharan
Summary: This research demonstrates that the Cu(111) surface state under wafer-scale hBN is homogeneous in energy and spectral weight over nanometer length scales and across atomic terraces. However, a new spectral feature that is not observed on bare Cu(111) varies with atomic registry and shares the spatial periodicity of the hBN/Cu(111) moire.
Article
Chemistry, Physical
Denis V. Lebedev, Vitaly A. Shkoldin, Alexey M. Mozharov, Artem O. Larin, V. Dmitry Permyakov, Anton K. Samusev, Anatoly E. Petukhov, Alexander O. Golubok, V. Alexander Arkhipov, Ivan S. Mukhin
Summary: This work presents a simple approach to fabricate nanoscale electrically driven light sources based on the phenomenon of light emission via inelastic tunneling of electrons. By using STM lithography, hybrid nanoantennas with a minimum diameter of 60 nm were formed, which can efficiently emit photons in the visible range.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Jindong Ren, Matthias Freitag, Yuxiang Gao, Peter Bellotti, Mowpriya Das, Bertram Schulze Lammers, Harry Monig, Yuyang Zhang, Constantin G. Daniliuc, Shixuan Du, Harald Fuchs, Frank Glorius
Summary: This study demonstrated the reversible self-assembly of cyclohexyl cyclic (alkyl)(amino)-carbenes and the importance of cyCAAC-surface interactions. By analyzing the molecular surface geometry and exploring various surfaces, the study deepened our understanding of cyCAAC binding mode and provided insights for catalysis, biosensor design, and surface functionalization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Kyohei Yamagata, Matsuhiro Maeda, Zeno Tessari, Kunal S. Mali, Yoshito Tobe, Steven De Feyter, Kazukuni Tahara
Summary: Grain boundaries in polycrystals significantly affect material properties, leading to research on grain boundary engineering. Using scanning tunneling microscopy, the authors observed quasi-periodic nanoscale chirality switching and twinning in self-assembled molecular networks at the liquid/solid interface. The width of the chiral domain structure peaked at 12-19 nm, and adjacent domains were connected through interdigitated alkoxy chains, forming a defect-free domain border.
Article
Multidisciplinary Sciences
Biao Yang, Martin Uphoff, Yi-Qi Zhang, Joachim Reichert, Ari Paavo Seitsonen, Andreas Bauer, Christian Pfleiderer, Johannes V. Barth
Summary: Iron silicide (FeSi) exhibits unusual electronic gap characteristics in the sub-10 K regime, with distinct features identified through high-resolution tunneling spectroscopy and density functional theory calculations. The DFT-calculated band structure provides insights into the origin of these features and supports the emergence of surface metallicity in the low-temperature regime.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2021)
Article
Chemistry, Multidisciplinary
Arne Merschel, Dennis Rottschaefer, Beate Neumann, Hans-Georg Stammler, Mark Ringenberg, Maurice Van Gastel, T. Ilgin Demirer, Diego M. M. Andrada, Rajendra S. S. Ghadwal
Summary: In this study, we have successfully synthesized and isolated two stable anions K[SIPrBp] (4 a-K) and K[IPrBp] (4 b-K). These anions, derived from classical N-heterocyclic carbenes (NHCs), exist as violet crystalline solids.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Bastiaan Kooij, Zhaowen Dong, Paul Varava, Farzaneh Fadaei-Tirani, Rosario Scopelliti, Laura Piveteau, Kay Severin
Summary: This study reports the preparation and structural characterization of vanadium complexes with N-heterocyclic vinylidene ligands, enabled by utilizing diazoolefins as ligand precursors. Structural and theoretical analysis show that N-heterocyclic vinylidenes can act as strong 6e(-) donor ligands, forming strong metal-carbon interactions.
CHEMICAL COMMUNICATIONS
(2022)
Article
Multidisciplinary Sciences
Shuyi Liu, Adnan Hammud, Ikutaro Hamada, Martin Wolf, Melanie Mueller, Takashi Kumagai
Summary: Coherent phonon spectroscopy is a method to study ultrafast lattice dynamics and its coupling to other degrees of freedom. In this study, nanoscale coherent phonon spectroscopy was achieved using ultrafast laser-induced scanning tunneling microscopy in a plasmonic junction. The localized excitation of coherent phonons in ultrathin zinc oxide films and their detection via photoinduced tunneling current through an electronic resonance allowed for the observation of nanoscale spatial variations in phonon dynamics that correlated with the distribution of electronic local density of states resolved by scanning tunneling spectroscopy.
Article
Chemistry, Analytical
Yufei Wang, Mingyang Li, Emma Gordon, Zhijiang Ye, Hang Ren
Summary: Understanding the structure-activity relationship in electrochemical metal dissolution reactions is crucial for designing higher density batteries and mitigating corrosions. The kinetics of metal dissolution is strongly influenced by surface structures, such as grain boundaries and defects. However, directly probing the electrochemical activity at these sites is challenging due to the limitation of conventional bulk electrochemistry. In this study, the colocalized mapping of an electrochemical metal dissolution reaction using Ag as a model system is reported. The local dissolution kinetics is measured using scanning electrochemical cell microscopy (SECCM) and correlated with the local structures obtained via colocalized electron backscattering diffraction (EBSD). The findings reveal the importance of nanoscale local electrochemical mapping and colocalized microscopic measurement in understanding the structure-activity relationship for electrochemical reactions at complex interfaces.
ANALYTICAL CHEMISTRY
(2022)
Editorial Material
Chemistry, Multidisciplinary
Guangying Tan, Frank Glorius
Summary: Stereochemical editing, a recently prominent method, enables direct manipulation of organic molecules with stereocenters to adjust their relative stereochemistry. Various light-driven reactions, such as deracemization and epimerization, have been successfully developed. Wendlandt and colleagues have recently reported a versatile photochemical epimerization of unactivated tertiary stereogenic centers, providing rapid access to challenging stereoisomers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Peter Bellotti, Huan-Ming Huang, Teresa Faber, Frank Glorius
Summary: The emergence of modern photocatalysis has revolutionized late-stage C-H functionalization, offering unprecedented regio- and chemoselectivities. This Review focuses on the strategies of small-molecule drugs, agrochemicals, and natural products, highlighting the main mechanistic scenarios and comparing established ionic chemistry and photocatalyzed radical-based manifolds. The authors aim to provide a comprehensive overview of the current state-of-the-art and address the challenges and future directions in this field.
Article
Chemistry, Multidisciplinary
Yujie Liang, Fritz Paulus, Constantin G. Daniliuc, Frank Glorius
Summary: We report a BF3-catalyzed [2 + 2] cycloaddition reaction between aldehydes and bicyclo[1.1.0]butanes (BCBs) to access polysubstituted 2-oxabicyclo[2.1.1]hexanes. A new BCB containing an acyl pyrazole group was discovered, which not only facilitates the reactions but also allows for diverse downstream transformations. Additionally, aryl and vinyl epoxides can be used as substrates that undergo cycloaddition with BCBs after in situ rearrangement to aldehydes. These results will promote the exploration of complex sp(3)-rich bicyclic frameworks and BCB-based cycloaddition chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Maurice Dellin, Ina Rohrbeck, Purva Asrani, Julian A. Schreiber, Nadine Ritter, Frank Glorius, Bernhard Wuensch, Thomas Budde, Louisa Temme, Timo Struenker, Birgit Stallmeyer, Frank Tuettelmann, Sven G. Meuth, Marc Spehr, Johann Matschke, Andrea Steinbicker, Christos Gatsogiannis, Raphael Stoll, Nathalie Strutz-Seebohm, Guiscard Seebohm
Summary: The study identified two binding sites, PS1 and S0, for PI(3,5)P-2 on the KCNQ1/KCNE1 channel, and found that binding of PI(3,5)P-2 to both sites is necessary for stabilizing the channel's open state.
BIOLOGICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Akash Kaithal, Himadri Sekhar Sasmal, Subhabrata Dutta, Felix Schafer, Lisa Schlichter, Frank Glorius
Summary: This study reports a catalytic approach to synthesizing cis-selective saturated carbo-and heterocyclic germanium compounds with a 3D framework through the hydrogenation of readily accessible aromatic germanes with a 2D framework. Nishimura's catalyst exhibited the best hydrogenation reactivity, achieving an isolated yield of up to 96%. The synthesized products showed versatile applications in coupling reactions and demonstrated orthogonal reactivity with boranes or silanes, acquiring a three-dimensional structure with high stability.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Roman Kleinmans, Subhabrata Dutta, Kristers Ozols, Huiling Shao, Felix Schafer, Rebecca E. Thielemann, Hok Tsun Chan, Constantin G. Daniliuc, Kendall N. Houk, Frank Glorius
Summary: The ortho-selective intermolecular photocycloaddition of bicyclic aza-arenes is reported, utilizing a strain-release approach. This reaction enables the construction of C-(sp(3))-rich bicyclo-[2.1.1]-hexanes directly connected to N-heteroarenes. Photophysical experiments and DFT calculations reveal the mechanism of this selective intermolecular photocycloaddition.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Yuquan Tong, Yeongju Lee, Xiaohui Liu, Jessica L. Childs-Disney, Blessy M. Suresh, Raphael I. Benhamou, Chunying Yang, Weimin Li, Matthew G. Costales, Hafeez S. Haniff, Sonja Sievers, Daniel Abegg, Tristan Wegner, Tiffany O. Paulisch, Elizabeth Lekah, Maison Grefe, Gogce Crynen, Montina Van Meter, Tenghui Wang, Quentin M. R. Gibaut, John L. Cleveland, Alexander Adibekian, Frank Glorius, Herbert Waldmann, Matthew D. Disney
Summary: Insufficient occupancy of the target, especially for RNA, leads to a lack of biological activity and the difficulty in recognizing RNA structures with small molecules adds to this challenge. By studying the molecular recognition patterns between a small-molecule collection and folded RNA structures, we can map the interaction landscapes across the human transcriptome and define structure-activity relationships. In cases where RNA-binding compounds bind elsewhere and are predicted to be biologically inert, an alternative strategy is to cleave the target through a ribonuclease-targeting chimera, using an RNA-binding molecule appended to a heterocycle that locally activates RNase L-1. Overlaying the substrate specificity of RNase L with the binding landscape of small molecules identifies potential bioactive binders that can be converted into degraders. Proof of concept is provided through the design of selective degraders for pre-miR-155, JUN mRNA, and MYC mRNA, demonstrating the potential of small-molecule RNA-targeted degradation as potent and specific modulators of RNA function.
Article
Chemistry, Multidisciplinary
Fritz Paulus, Colin Stein, Corinna Heusel, Tobias J. Stoffels, Constantin G. Daniliuc, Frank Glorius
Summary: In this study, a novel three-component 1,2,5-trifunctionalization reaction driven by visible light energy transfer-catalysis was reported. Selective installation of three different functional groups was achieved in one step by utilizing imine-based bifunctional reagents and two distinct alkenes. Mechanistic studies and downstream modifications demonstrated the synthetic utility of the obtained products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Peter Bellotti, Frank Glorius
Summary: The concept of strain in organic compounds is essential for understanding the synthesis and properties of organic compounds. Recent advancements in strain-release reactions and photocatalysis have opened up new possibilities for creating unique chemical architectures and expanding the field of strain research.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Huamin Wang, Johannes E. Erchinger, Madina Lenz, Subhabrata Dutta, Constantin G. Daniliuc, Frank Glorius
Summary: This study presents a photoredox strategy that enables the high regio- and syn-selective difunctionalization of bicyclo[1.1.0]-butanes (BCBs). By cleaving C-S sigma bonds, sulfur-alkynylation, -alkenylation, and -allylation of BCBs can be achieved under mild conditions, demonstrating the generality of this approach.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Huamin Wang, Huiling Shao, Ankita Das, Subhabrata Dutta, Hok Tsun Chan, Constantin Daniliuc, K. N. Houk, Frank Glorius
Summary: In this study, a photoinduced ring enlargement method of thiophenes was developed, which involves the insertion of bicyclo[1.1.0]butanes to form eight-membered bicyclic rings under mild conditions. The synthetic value, broad functional-group compatibility, and excellent chemo- and regioselectivity were demonstrated by scope evaluation and product derivatization. Experimental and computational studies suggested a photoredox-induced radical pathway.
Review
Chemistry, Multidisciplinary
Lukas Lueckemeier, Marco Pierau, Frank Glorius
Summary: This review aims to present the state-of-the-art in transition-metal catalysed asymmetric hydrogenation of (hetero)arenes, highlighting recent advances and important trends, and providing a broad overview for the reader.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Organic
Tristan Wegner, Anna L. L. Matos, Karine Porte, Kira Mehring, Marco Pierau, Hendrik Horstmeier, Volker Gerke, Frank Glorius
Summary: Cholesterol is a vital lipid in cellular membranes and plays a role in various cellular processes. Diseases like immunological disorders and cancer have been associated with abnormalities in cholesterol homeostasis. Thus, there is a need for molecular tools to study cholesterol distribution and interactions. In this study, a novel bifunctional imidazolium-based cholesterol analog (X-CHIM) was synthesized, which can serve as a versatile tool for investigating cellular cholesterol distributions and cholesterol-protein interactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Materials Science, Multidisciplinary
Robert Zielinski, Mowpriya Das, Canan Kosbab, Mike Thomas Nehring, Mario Daehne, Norbert Esser, Martin Franz, Frank Glorius
Summary: The adsorption behavior of cyclohexyl cyclic (alkyl)(amino)carbene molecules on a silicon surface is investigated, showing a self-limited, well ordered growth of a stable monolayer with large domains, which is surprising on semiconductors. Additionally, the surface defect density strongly influences the grade of ordering, as the initial adsorption takes place on a defect site.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Florenz Buss, Mowpriya Das, Daniel Janssen-Mueller, Alexander Sietmann, Ankita Das, Lukas F. B. Wilm, Matthias Freitag, Michael Seidl, Frank Glorius, Fabian Dielmann
Summary: This study reports the synthesis and properties of photoswitchable electron-rich phosphines containing N-heterocyclic imines. Heteronuclear NMR spectroscopy and UV/vis studies reveal reversible electrocyclic ring-closing and ring-opening reactions of the imine substituents upon exposure to UV and visible light. The photoisomerization alters the electron-donating ability of the phosphines by up to Delta TEP = 8 cm-1.
CHEMICAL COMMUNICATIONS
(2023)
