Article
Chemistry, Multidisciplinary
Anni Shi, Terry A. Villarreal, Anamika Singh, Tyler R. Hayes, Tyson C. Davis, Jacob T. Brooks, Shelley A. Claridge
Summary: Researchers have identified a previously unreported difference in polymerization efficiency between two widely used commercial diynoic acids using a new multi-scale approach. They have also discovered a core design principle for maximizing polymerization efficiency in these on-surface reactions and developed a new monomer with enhanced polymerization efficiency.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Vesselin Donchev, Davide Regaldo, Stefan Georgiev, Aleksandra Bojar, Mattia da Lisca, Kiril Kirilov, Jose Alvarez, Philip Schulz, Jean -Paul Kleider
Summary: In this study, perovskite (PVK) films deposited directly on n-type crystalline Si substrates were investigated using two operating modes of the surface photovoltage (SPV) method: the metal-insulator-semiconductor (MIS) mode and the Kelvin probe force microscopy (KPFM). The MIS mode allowed for a consecutive study of carrier generation, transport, and recombination processes in Si, PVK/Si interface, and the PVK layer and its surface. The PVK optical absorption edge and energy band bending at the PVK/n-Si interface were observed and analyzed. Aging effects on the PVK/n-Si interface were also studied.
Article
Chemistry, Multidisciplinary
Zachary T. Gossage, Nanako Ito, Tomooki Hosaka, Ryoichi Tatara, Shinichi Komaba
Summary: This study provides a deeper understanding of the solid-electrolyte interphase (SEI) that occurs in highly concentrated water-insalt electrolytes (WISEs). The research shows that SEI in aqueous batteries exhibits similar passivating structures and slow electron transfer rates to that found in lithium-ion batteries. Additionally, the properties of SEI change when the electrolyte becomes more concentrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Vijai M. Santhini, Christian Wackerlin, Ales Cahlik, Martin Ondracek, Simon Pascal, Adam Matej, Oleksandr Stetsovych, Pingo Mutombo, Petr Lazar, Olivier Siri, Pavel Jelinek
Summary: Recently, there has been significant interest in pi-d conjugated coordination polymers due to their unique material properties, although synthesizing long and defect-free polymers remains challenging. A novel on-surface synthesis method using quinoidal ligands under ultra-high vacuum conditions has been introduced, enabling the formation of flexible coordination polymers with lengths up to hundreds of nanometers. This method also allows for the incorporation of different transition-metal atoms with four- or two-fold coordination, revealing the formation of wires constituted by independent 12-membered antiaromatic macrocycles linked together through two C-C single bonds in the two-fold coordination mode.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Georg H. Simon, Christopher S. Kley, Beatriz Roldan Cuenya
Summary: Electrochemical AFM is an effective tool for real-space characterization of catalysts under CO2RR conditions, revealing the complex interplay between morphology, structure, defect density, applied potential, and electrolyte in copper CO2RR catalysts. The study showed distinct nanoscale surface morphologies and their potential-dependent transformations during CO2RR on a Cu(100) model surface in 0.1 m KHCO3. In situ atomic-scale imaging identified specific adsorption at different cathodic potentials impacting the catalyst structure.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Waseem A. Hussain, Kyle N. Plunkett
Summary: New conjugated polymers containing dihexylanthradithiophene (DHADT) in the main chain were successfully synthesized by Stille, Sonogashira, and Yamamoto cross-coupling polymerization reactions. These polymers exhibit notable optical features and are suitable for use in organic field effect transistors.
Article
Chemistry, Multidisciplinary
James Lawrence, Mohammed S. G. Mohammed, Dulce Rey, Fernando Aguilar-Galindo, Alejandro Berdonces-Layunta, Diego Pena, Dimas G. de Oteyza
Summary: This study investigates the reaction pathways and product structures on an Au(111) surface using a pyrene-based precursor with alkyne and halogen functional groups, revealing the relationship between reaction activity and product structures through scanning tunneling spectroscopy.
Article
Nanoscience & Nanotechnology
Benjamin Mallada, Piotr Blonski, Rostislav Langer, Pavel Jelinek, Michal Otyepka, Bruno de la Torre
Summary: By combining experimental and theoretical studies, a method for growing one-dimensional metalloporphyrin polymers on surfaces and tuning their magnetic properties has been discovered, providing new opportunities for realizing and studying well-defined one-dimensional organic magnets.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Multidisciplinary
Kwan Ho Au-Yeung, Tim Kuehne, Daniel Becker, Marcus Richter, Dmitry A. Ryndyk, Gianaurelio Cuniberti, Thomas Heine, Xinliang Feng, Francesca Moresco
Summary: The rapid development of on-surface synthesis has provided a unique approach for the formation of carbon-based nanostructures with designed properties. In this study, CN-substituted phenylene vinylene chains were formed on the Au(111) surface by stepwise annealing the substrate at temperatures between 220°C and 240°C. The formation of these chains was attributed to a Knoevenagel condensation reaction between an aldehyde and a methylene nitrile substituent, as supported by scanning tunneling microscopy and density functional theory.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Biao Yang, Kaifeng Niu, Nan Cao, Nitika Grover, Wenchao Zhao, Alexander Riss, Jonas Bjoerk, Willi Auwaerter, Johannes V. Barth, Mathias O. Senge
Summary: In this study, the behavior of 1,3-disubstituted BCP moieties on metal surfaces was examined using low-temperature scanning tunneling microscopy/non-contact atomic force microscopy studies and density functional theory modeling. The configuration, supramolecular assembly, and thermally activated dehalogenative coupling reactions of BCP-containing precursors on Au(111) were investigated, resulting in the formation of polymeric chains. These findings provide sub-molecular insights into the behavior of BCP scaffolds on surfaces and expand the potential application of BCP derivatives in custom-designed surface architectures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Minhui Lee, Emiko Kazuma, Jaehoon Jung, Michael Trenary, Yousoo Kim
Summary: A detailed understanding of the dissociation of O-2 molecules on metal surfaces is crucial for controlling oxidation reactions and developing catalysts. Single-molecule studies using a scanning tunneling microscope provide fundamental insights into the excitation pathway for dissociation reactions.
Review
Chemistry, Physical
Sanjay Sahare, Prachi Ghoderao, Peng Yin, Awais Siddique Saleemi, Shern-Long Lee, Yue Chan, Han Zhang
Summary: The exploration of the unique properties of 2D materials, including MXenes, has become a new wave of research. This review provides a comprehensive overview of the preparation methods and material analysis of MXenes. It also discusses the challenges and perspectives for the application of MXenes in various fields.
Article
Computer Science, Artificial Intelligence
Yongtao Liu, Rama K. Vasudevan, Kyle K. Kelley, Dohyung Kim, Yogesh Sharma, Mahshid Ahmadi, Sergei Kalinin, Maxim Ziatdinov
Summary: The shift-VAE is an unsupervised method for analyzing spectral data in the presence of shifts along the parameter axis, with applications in various fields such as band-excitation piezoresponse force microscopy data analysis, denoising of data, and model-free dimensionality reduction in imaging and spectroscopic data.
MACHINE LEARNING-SCIENCE AND TECHNOLOGY
(2021)
Article
Chemistry, Physical
Diane M. Haiber, Barnaby D. A. Levin, Michael M. J. Treacy, Peter A. Crozier
Summary: Graphitic carbon nitrides are important materials for energy conversion processes, but structural disorder hinders the prediction of structure-property relationships. Low-fluence-rate transmission electron microscopy and analysis of local Patterson functions reveal fluctuations in the in-plane structures and their relationship to polymer chain lengths. Shorter chains are associated with higher amine content, and investigation of 3D stacking sequence shows turbostratic stacking disorder. These insights help in constructing accurate structure models and predicting catalytic properties of g-CNxHy.
CHEMISTRY OF MATERIALS
(2021)
Article
Multidisciplinary Sciences
Xuezhi Ma, Qiushi Liu, Ning Yu, Da Xu, Sanggon Kim, Zebin Liu, Kaili Jiang, Bryan M. Wong, Ruoxue Yan, Ming Liu
Summary: Optical transmission and scattering spectroscopic microscopy is limited by the diffraction limit of light, but a super-resolution hyperspectral imaging technique has been developed to achieve 6 nm spatial resolution in single-walled carbon nanotubes. This technique allows for measurement of optical electronic transitions and chiral indices in nanomaterials.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ana Barragan, Tomas Nicolas-Garcia, Koen Lauwaet, Ana Sanchez-Grande, Jose Urgel, Jonas Bjork, Emilio M. Perez, David Ecija
Summary: Nanocars are carbon-based single-molecules that can be precisely controlled on a surface at the atomic scale. The design of these molecules plays a crucial role in advancing the development of molecular machines and understanding self-assembly and other processes. In this study, we present the design and construction of a collection of minimalistic nanocars featuring an anthracene chassis and benzene derivatives as wheels. By using a scanning tunneling microscope (STM) tip to induce a dipole in the nanocar, we were able to manipulate it along the surface, achieving controlled and rapid displacement. The use of carbon monoxide functionalized tips prevented decomposition and accidental picking up of the nanocars during manipulation, leading to our success in the Nanocar Race II championship.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kalyan Biswas, Diego Soler, Shantanu Mishra, Qiang Chen, Xuelin Yao, Ana Sanchez-Grande, Kristjan Eimre, Pingo Mutombo, Cristina Martin-Fuentes, Koen Lauwaet, Jose M. Gallego, Pascal Ruffieux, Carlo A. Pignedoli, Klaus Mullen, Rodolfo Miranda, Jose I. Urgel, Akimitsu Narita, Roman Fasel, Pavel Jelinek, David Ecij
Summary: This study explores three families of nanographenes (A, B, and C) and finds that open-shell nanographenes exhibit the strongest magnetic exchange coupling, especially near the transition from closed-shell to open-shell states. Experimental results confirm the predictions, and two specific nanographenes show record values of magnetic exchange coupling measured on the Au(111) surface, close to 200 meV. This research provides insights for designing carbon nanomaterials with robust magnetic ground states.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Alejandro Jimenez-Martin, Federico Villalobos, Benjamin Mallada, Shayan Edalatmanesh, Adam Matej, Juan M. Cuerva, Pavel Jelinek, Araceli G. Campana, Bruno de la Torre
Summary: We present a new on-surface synthetic approach for incorporating five-membered rings into conjugated polymers, resulting in low-bandgap fulvalene-bridged bisanthene polymers. The formation of non-benzenoid units is controlled by annealing parameters, which facilitate the transformation of diethynyl bridges into fulvalene moieties. The atomically precise structures and electronic properties are characterized using STM, nc-AFM, STS, and supported by DFT calculations. The narrow frontier electronic gaps of 1.2 eV observed on Au(111) suggest the potential of this strategy in tuning optoelectronic properties by integrating five-membered rings at specific sites in other conjugated polymers.
Article
Chemistry, Multidisciplinary
Biao Yang, Kaifeng Niu, Nan Cao, Nitika Grover, Wenchao Zhao, Alexander Riss, Jonas Bjoerk, Willi Auwaerter, Johannes V. Barth, Mathias O. Senge
Summary: In this study, the behavior of 1,3-disubstituted BCP moieties on metal surfaces was examined using low-temperature scanning tunneling microscopy/non-contact atomic force microscopy studies and density functional theory modeling. The configuration, supramolecular assembly, and thermally activated dehalogenative coupling reactions of BCP-containing precursors on Au(111) were investigated, resulting in the formation of polymeric chains. These findings provide sub-molecular insights into the behavior of BCP scaffolds on surfaces and expand the potential application of BCP derivatives in custom-designed surface architectures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Daniel Moreno, Jose Santos, Sofia O. Parreiras, Cristina Martin-fuentes, Koen Lauwaet, Jose I. Urgel, Rodolfo Miranda, Nazario Martin, Jose M. Gallego, David Ecija
Summary: The control of hierarchical growth is crucial for the formation of two-dimensional supramolecular porous networks on gold surfaces, especially for lanthanide-based architectures.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Physics, Condensed Matter
Federico Frezza, Ana Sanchez-Grande, Martin Ondracek, Martin Vondracek, Qifan Chen, Oleksandr Stetsovych, Victor Villalobos-Vilda, Ezequiel Tosi, Francisco Javier Palomares, Maria Francisca Lopez, Carlos Sanchez-Sanchez, Karl-Heinz Ernst, Jose Angel Martin-Gago, Jan Honolka, Pavel Jelinek
Summary: We investigate the atomic structure and electronic properties of epitaxial SnSe structures grown on a metallic Au(111) substrate. We observe a coverage-dependent transition from metallic beta-SnSe to semiconducting alpha-SnSe phases. Comprehensive characterization techniques, combined with density functional theory, allow us to study the geometric and electronic properties of both phases.
JOURNAL OF PHYSICS-CONDENSED MATTER
(2023)
Article
Chemistry, Multidisciplinary
Xuechao Li, Kaifeng Niu, Sai Duan, Yanning Tang, Zhengming Hao, Zhichao Xu, Haitao Ge, Johanna Rosen, Jonas Bjork, Haiming Zhang, Xin Xu, Lifeng Chi
Summary: In this study, the acetylenic homocoupling reaction of polarized terminal alkynes on Au(111) was examined using bond-resolved scanning probe microscopy. The replacement of benzene with pyridine moieties effectively inhibited the cyclotrimerization pathway and promoted linear coupling to produce well-aligned N-doped graphdiyne nanowires. Density functional theory calculations revealed that the pyridinic nitrogen modification significantly influenced the coupling motifs at the initial C-C coupling stage (head-to-head vs head-to-tail), which determined the preference of linear coupling over cyclotrimerization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Tao Wang, Paula Angulo-Portugal, Alejandro Berdonces-Layunta, Andrej Jancarik, Andre Gourdon, Jan Holec, Manish Kumar, Diego Soler, Pavel Jelinek, David Casanova, Martina Corso, Dimas G. de Oteyza, Jan Patrick Calupitan
Summary: The coupling of a sterically demanded pentacene derivative on Au(111) into fused dimers connected by non-benzenoid rings was studied using high-resolution scanning tunneling microscopy/spectroscopy and density functional theory. The diradical character of the products was tuned by modifying the coupling section, with the antiaromaticity of cyclobutadiene and its position within the structure playing a significant role. Understanding these structure-property relationships is crucial for designing new complex and functional molecular structures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Nan Cao, Biao Yang, Alexander Riss, Johanna Rosen, Jonas Bjork, Johannes V. Barth
Summary: Enetriynes, a distinct class of highly conjugated pi-system compounds, are formed with high selectivity by tetramerization of terminal alkynes on Ag(100) surface. The formation is induced by O-2 exposure, resulting in deprotonation of terminal alkyne moieties and the evolution of organometallic bis-acetylide dimer arrays. Subsequent thermal annealing leads to the generation of tetrameric enetriyne-bridged compounds, which readily self-assemble into regular networks. High-resolution scanning probe microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations are employed to examine the structural features, bonding characteristics, and reaction mechanism.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Nan Cao, Jonas Bjoerk, Eduardo Corral-Rascon, Zhi Chen, Mario Ruben, Mathias O. Senge, Johannes V. Barth, Alexander Riss
Summary: This study investigates how aromaticity affects the reactivity of alkyne-substituted porphyrin molecules on a Au(111) surface. The experiments show that carbon atoms stabilized by aromaticity display lower reactivity, which is consistent with density functional theory calculations.
Article
Chemistry, Multidisciplinary
Khabib Yusupov, Jonas Bjork, Johanna Rosen
Summary: Functional 2D materials show varied properties influenced by surface terminations. This study focuses on the influence of termination species (O, NH, N, S, F, Cl, Br, I) on the electronic structure, work function, dynamical stability, and atomic charges and distances of MXenes. It was found that the work function generally decreases with reduced electronegativity of the terminating species, except for NH terminations which display a significantly reduced work function due to an intrinsic dipole moment. Halogen terminations were found to improve the electrical conductivity of the materials.
NANOSCALE ADVANCES
(2023)
Article
Chemistry, Multidisciplinary
Sofia O. Parreiras, Daniel Moreno, Shanmugasibi K. Mathialagan, Beatriz Muniz-Cano, Cristina Martin-Fuentes, Maria Tenorio, Lenka Cerna, Jose I. Urgel, Koen Lauwaet, Manuel Valvidares, Miguel A. Valbuena, Jose M. Gallego, Jose I. Martinez, Pierluigi Gargiani, Rodolfo Miranda, Julio Camarero, David Ecija
Summary: The coordination of lanthanides atoms in two-dimensional surface-confined metal-organic networks is a promising path to achieve an ordered array of single atom magnets. Here we introduce an Er-directed two-dimensional metallosupramolecular network on Cu(111) featuring strong out-of-plane magnetic anisotropy. Our results will contribute to pave avenues for the use of lanthanides in potential applications in nanomagnetism and spintronics.
Article
Chemistry, Multidisciplinary
Alejandro Berdonces-Layunta, Adam Matej, Alejandro Jimenez-Martin, James Lawrence, Mohammed S. G. Mohammed, Tao Wang, Benjamin Mallada, Bruno de la Torre, Adrian Martinez, Manuel Vilas-Varela, Reed Nieman, Hans Lischka, Dana Nachtigallova, Diego Pena, Pavel Jelinek, Dimas G. de Oteyza
Summary: The study demonstrates the sensitivity of graphene nanoribbon zigzag edges to water, showing that water can hydrogenate the central carbon of the zigzag segments. This effect can be reversed by tip manipulation and annealing. The results also show a periodic pattern of spontaneous hydrogenation of gold-supported chiral graphene nanoribbons even at room temperature.
Article
Chemistry, Multidisciplinary
Alejandro Jimenez-Martin, Aurelio Gallardo, Bruno de la Torre
Summary: This study proposes a strategy for tuning the directionality of self-assembly processes in homomolecular organic compounds on inert metal surfaces. The results reveal a halogen-bond geometry transformation induced by a subtle balance of molecule-molecule interaction. Furthermore, the research finds that the halogen-bonded supramolecular assembly can periodically confine electronic quantum states and single atoms.
Article
Chemistry, Multidisciplinary
Diego J. Vicent, Manuel Perez-Escribano, Abel Cardenas-Valdivia, Ana Barragan, Joaquin Calbo, Jose I. Urgel, David Ecija, Jose Santos, Juan Casado, Enrique Orti, Nazario Martin
Summary: This study focuses on the investigation of relatively unknown tetrabromo-p-quinodimethanes (TBQs) as molecular building blocks. Five derivatives incorporating tetrabromo-anthraquinodimethane (TBAQ) units are showcased, revealing their warped geometry and complex NMR pattern. The study also assesses the sublimation, self-assembly, and reactivity of TBQ3 on Au(111).
