Article
Chemistry, Multidisciplinary
Ludwig Zapf, Sven Peters, Ruediger Bertermann, Udo Radius, Maik Finze
Summary: This study demonstrates that the charge, coordination site number, volume, σ-donor, and π-acceptor properties of NHCs can be effectively tuned by the number of tricyanoborane substituents.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Shahar Dery, Israel Alshanski, Evgeniy Mervinetsky, Daniel Feferman, Shlomo Yitzchaik, Mattan Hurevich, Elad Gross
Summary: The study investigated the impact of surface-adsorbate interactions on the adsorption geometry of stilbene-NHCs monolayers and its influence on surface potential. It was found that stilbene-NHCs on Au film accumulated in a vertical orientation for high photoisomerization efficiency, while strong metal-adsorbate interactions on Pt film led to a flat-lying adsorption geometry that quenched the photo-induced response.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Iris Berg, Lillian Hale, Mazal Carmiel-Kostan, F. Dean Toste, Elad Gross
Summary: N-Heterocyclic carbenes (NHCs) were functionalized with a triisopropylsilyl (TIPS)-protected alkyne group and self-assembled on Au films to enable post-deposition functionalization by C-C coupling reactions. The TIPS group efficiently protected the alkyne and prevented its deprotonation during surface-anchoring of NHC. Sonogashira C-C coupling reactions were performed on the Au film in high yield following removal of the TIPS group, demonstrating that post-deposition coupling reactions can be employed to widen the chemical scope of surface-anchored NHCs.
CHEMICAL COMMUNICATIONS
(2021)
Review
Biochemistry & Molecular Biology
Vincent Ritleng, Christophe Michon
Summary: This review focuses on the application of ruthenium complexes with bidentate donor-functionalized N-heterocyclic carbene ligands in catalyzing hydrogen transfer reactions, and discusses the effects of different donor atoms and carbene ligands on the transfer hydrogenation reactions. This research is important for improving the efficiency and selectivity of catalytic hydrogen transfer reactions.
Article
Polymer Science
Kuen Hee Eom, Seokhyeon Baek, Il Kim
Summary: Synthetic polypeptides prepared from N-carboxyanhydrides are useful for investigating the relationship between the primary structure of natural peptides and their immunogenicity. The random copolymerization of different NCAs using N-heterocyclic carbene catalysts produced copolypeptides with specific sequences, showing rich alternating units in some cases.
Article
Chemistry, Physical
Diep T. H. Nguyen, Marilyne Belanger-Bouliga, Lorianne R. Shultz, Arunava Maity, Titel Jurca, Ali Nazemi
Summary: Gold nanomaterials have been traditionally stabilized and functionalized by sulfur-containing ligands, but there is recent interest in using N-Heterocyclic carbenes (NHCs) as alternative stabilizers. This study introduces polymeric mesoionic NHC-Au(I) complexes as precursors to stable AuNPs, which demonstrate exceptional stability against harsh conditions and high concentrations of glutathione in aqueous media. Furthermore, the use of macromolecular substrates leads to the formation of larger AuNPs with enhanced stabilities, showing promise for applications in nanomedicine.
CHEMISTRY OF MATERIALS
(2021)
Article
Chemistry, Inorganic & Nuclear
Xin Li, Jing Zhao, Wen-Jie Shi, Sha Bai, Ying-Feng Han
Summary: Three coinage-metal NHC complexes with picolyl-functionalized NHC ligands were synthesized, showing different geometries depending on the coordination modes of the multidentate ligand towards the metal ions. The trinuclear Ag-I complex was directly synthesized by one-step reaction, while unexpected copper(I)-NHC and tetranuclear gold(I) complexes were formed through transmetalation. Anion-induced structural transformation further led to the formation of two trinuclear gold(I)-NHC complexes.
Article
Multidisciplinary Sciences
Chengtao Yue, Qi Xing, Peng Sun, Zelun Zhao, Hui Lv, Fuwei Li
Summary: The study successfully stabilized palladium in heterogeneous C-C bond formations by developing a novel bifunctional support catalyst, providing new experimental evidence for improving the stability of catalysts and enhancing the efficient applications of supported metal catalysts in advanced synthesis.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Yuying Chai, Yaling Li, Hui Hu, Chaoyuan Zeng, Shenglin Wang, Huanjun Xu, Yanan Gao
Summary: The integration of N-Heterocyclic carbene (NHC) moiety into a covalent organic framework (COF) resulted in a material with promising heterogeneous catalytic activity towards transesterification reactions. The material exhibited good recyclability with no substantial loss of activity over five cycles. The combination of COFs and NHCs may synergize their characteristics and offer more possibilities for catalytic reactivity.
Article
Nanoscience & Nanotechnology
Yunsoo Choi, Chul Soon Park, Hung-Vu Tran, Chien-Hung Li, Cathleen M. Crudden, Randall Lee
Summary: This study reports the development and use of bench-stable NHC adsorbates for the direct formation of NHC films on gold surfaces under ambient conditions. The generated NHC SAMs were fully characterized and compared to analogous SAMs generated from a different adsorbate. Furthermore, the potential utility of these NHC films as surface-initiated polymerization platforms was demonstrated.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Hang Shen, Michael B. Larsen, Allison G. Roessler, Paul M. Zimmerman, Andrew J. Boydston
Summary: A new flex-activated mechanophore has been discovered, which releases an N-heterocyclic carbene (NHC) under mechanical load. This design demonstrates a promising first step towards flex-activated designs with downstream reactivities, allowing for iterative activation increases in the material through non-destructive compression cycles. The potential modularity of the mechanophore design is highlighted by the demonstration of two different NHC structures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Gurkiran Kaur, Rebekah L. Thimes, Jon P. Camden, David M. Jenkins
Summary: The discovery of N-heterocyclic carbenes (NHCs) has revolutionized organometallic chemistry by providing strong metal-ligand bonds. This review article highlights the applications of NHCs on gold surfaces and nanoparticles, focusing on their enhanced stability and synthetic tunability. Unique scientific questions and new applications in biomedicine, catalysis, and microelectronics are also discussed.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Rita Lopes, Alvaro Raya-Baron, M. Paula Robalo, Carolina Vinagreiro, Sonia Barroso, Maria J. Romao, Ignacio Fernandez, Mariette M. Pereira, Beatriz Royo
Summary: Two piano-stool iron(II) complexes with N-heterocyclic carbene ligands were synthesized and studied for their catalytic activity in the transfer hydrogenation of ketones. Complex 3 exhibited the highest catalytic activity among the series, with a TOF(50) value of 533 h(-1). A new species 3' containing a deprotonated amidate moiety was identified through NMR monitoring, and a green protocol for ketone reduction using glycerol as a hydrogen source and microwave irradiation with catalytic amounts of complex 3 and base was developed.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Shin Ando, Akio Ohara, Tomohiko Ohwada, Tadao Ishizuka
Summary: A new type of saturated N-heterocyclic olefin was synthesized and its rhodium and palladium complexes were obtained. Studies revealed that the metal complexes of the saturated NHO exhibited isomerization in solution. Computational studies emphasized the importance of the N-substituent for the planarity of the NHO and its metal complexes.
Article
Chemistry, Organic
Zhen Li, Pengju Ji, Jin-Pei Cheng
Summary: A Brønsted basicity scale was established for nine representative N-heterocyclic olefins (NHOs) using an UV-visible spectroscopic method. The unsaturated NHOs were found to have stronger basicities compared to their N-heterocyclic carbene (NHC) analogues, while the basicities of the saturated NHOs were weaker. The nucleophilicity of the NHOs was also stronger than commonly used Lewis bases but weaker than their NHC analogues.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Iulia Cojocariu, Silvia Carlotto, Henning Maximilian Sturmeit, Giovanni Zamborlini, Mirko Cinchetti, Albano Cossaro, Alberto Verdini, Luca Floreano, Matteo Jugovac, Peter Puschnig, Cinthia Piamonteze, Maurizio Casarin, Vitaliy Feyer, Claus Michael Schneider
Summary: Iron phthalocyanine has unique magnetic properties due to the open-shell electronic structure of the central metal ion, making it a valuable catalyst in various reactions. Surface deposition on Cu(100) alters the charge distribution and magnetic properties of the molecule, affecting the spin state of the iron ion. Exposure to different doses of NO2 at room temperature at the metalorganic/metal interface results in three different spin configurations, demonstrating the tunability of the magnetic properties of the iron ion.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Alessio Orbelli Biroli, Alberto Calloni, Alberto Bossi, Madan S. Jagadeesh, Guglielmo Albani, Lamberto Duo, Franco Ciccacci, Andrea Goldoni, Alberto Verdini, Luca Schio, Luca Floreano, Gianlorenzo Bussetti
Summary: The study demonstrates the growth of a coherent 2D+n layered heterorganic film on a metal electrode through chemical decoupling, commensurate 2D ordering, rigid molecule-to-molecule coupling guided by SA coordination chemistry, and sharp termination of the layered film.
ADVANCED FUNCTIONAL MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Matus Stredansky, Stefania Moro, Manuel Corva, Henning Sturmeit, Valentin Mischke, David Janas, Iulia Cojocariu, Matteo Jugovac, Albano Cossaro, Alberto Verdini, Luca Floreano, Zhijing Feng, Alessandro Sala, Giovanni Comelli, Andreas Windischbacher, Peter Puschnig, Chantal Hohner, Miroslav Kettner, Jorg Libuda, Mirko Cinchetti, Claus Michael Schneider, Vitaliy Feyer, Erik Vesselli, Giovanni Zamborlini
Summary: Uncommon metal oxidation states in porphyrinoid cofactors play a crucial role in the activity of many enzymes. This study provides experimental and theoretical evidence on the reaction of nickel porphyrins with nitric oxide, and offers a detailed interpretation of the measurements.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Physics, Condensed Matter
Giovanni Carraro, Marco Smerieri, Simone Passaglia, Gianangelo Bracco, Luca Vattuone, Mario Rocca, Albano Cossaro, Alberto Verdini, Luca Floreano, Letizia Savio
Summary: This study investigates the adsorption behavior of glutamic acid on TiO2 surface and finds that surface hydroxylation affects the adsorption state. It is suggested that glutamic acid binds to the surface through a carboxylate group.
JOURNAL OF PHYSICS-CONDENSED MATTER
(2022)
Article
Chemistry, Physical
Pierre-Marie Deleuze, Helene Magnan, Antoine Barbier, Zheshen Li, Alberto Verdini, Luca Floreano, Bruno Domenichini, Celine Dupont
Summary: In this paper, synchrotron radiation photoemission techniques were used to investigate the properties of the Ba 4d components, Ba(alpha) and Ba(beta). Different behaviors were observed for Ba(alpha) and Ba(beta) in photoelectron diffraction experiments. DFT calculations supported the findings, showing that Ba(alpha) mainly originates from the topmost BaO layer, while Ba(beta) comes predominantly from the surface BaO plane.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Suhong Kim, Pan-Pan Chen, K. N. Houk, Robert R. Knowles
Summary: This study presents a case of catalytic carbon-carbon sigma-bond homolysis achieved through coordination-induced bond-weakening effect, with a ruthenium redox couple used for bond weakening. Experimental and computational analysis revealed the stereospecificity of the isomerization reaction and quantified the bond-weakening effect through transition state analysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Analytical
Linoy Dery, Shahar Dery, Elad Gross, Daniel Mandler
Summary: The study investigates NP-electrode electrostatic interactions by tracking the oxidation of AgNPs at charged self-assembled monolayer (SAM) functionalized Au microelectrodes. The results show that repulsive electrostatic interactions decrease collision frequency and lead to erroneous nanoparticle sizing, while attractive electrostatic interactions significantly increase collision frequency and extend sizing capability.
ANALYTICAL CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Shahar Dery, Barak Friedman, Hadar Shema, Elad Gross
Summary: The recent development of high spatial resolution microscopy and spectroscopy tools has allowed for the analysis of reactions in (electro)catalysts at previously unattainable resolution and sensitivity. These studies have revealed that catalysts are more heterogeneous than expected, with variations in active sites leading to differences in reaction mechanisms. This review highlights recent insights gained from high spatial resolution studies, including the detection of reactivity in single particles or molecular catalysts and the analysis of catalyst distribution and accessibility on overall reactivity. It is emphasized that the integration of spectroscopy and microscopy measurements under realistic reaction conditions is essential for bridging the gap between model systems and real-world catalysis research.
Article
Chemistry, Physical
Jose Abad, Jose I. Martinez, Paula Gomez, Miriam Mas-Montoya, Luis Rodriguez, Albano Cossaro, Alberto Verdini, Luca Floreano, Jose A. Martin-Gago, David Curiel, Javier Mendez
Summary: The control of molecular structures at the nanoscale is crucial for material and application development. The adsorption of a polyheteroaromatic molecule on Au(111) has been studied, revealing the formation of highly organized linear structures due to intermolecular hydrogen bonding. Different arrangements, including extended brick-wall and herringbone packing, were observed. Comprehensive experimental and theoretical characterizations were conducted to study the 2D hydrogen-bonded domains and the on-surface thermal stability of the physisorbed material.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Nerea Ruiz del arbol, Carlos Sanchez-Sanchez, Jose I. Martinez, Luis Rodriguez, David Serrate, Alberto Verdini, Luca Floreano, Peter Jacobson, Leonhard Grill, Jose A. Martin-Gago, Maria F. Lopez
Summary: Two different metal-organic frameworks were grown on Cu(111) with different structures, a honeycomb or Kagome structure, using para-aminophenol molecules and native surface adatoms. Despite the same chemical species, their structural difference highlights the critical role of reaction conditions during growth. This work emphasizes the importance of balancing thermodynamics and kinetics in the final structure of surface-supported metal-organic networks.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Silvia Carlotto, Alberto Verdini, Giovanni Zamborlini, Iulia Cojocariu, Vitaliy Feyer, Luca Floreano, Maurizio Casarin
Summary: A precise understanding of the charge transfer at the NiTPP/Cu(100) interface has been gained through symmetry considerations and photoelectron diffraction measurements. The chemisorption site of NiTPP on Cu(100) has been determined, and the interfacial charge transfer has been revealed.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Alessandro Sala, Maria Caporali, Manuel Serrano-Ruiz, Francesco Armillotta, Erik Vesselli, Francesca Genuzio, Tevfik Onur Mente, Andrea Locatelli, Giovanni Comelli, Cristina Africh, Alberto Verdini
Summary: Phosphorene, a single-layer black phosphorus, is emerging as a promising material in the field of (2D) semiconductors due to its high carrier mobility and anisotropic structure. This study demonstrates that both black and red phosphorus deposition on a gold substrate result in the formation of the same blue phosphorene film.
Article
Chemistry, Physical
Pierre-Marie Deleuze, Helene Magnan, Antoine Barbier, Zheshen Li, Alberto Verdini, Luca Floreano, Bruno Domenicuni, Celine Dupont
Summary: In this study, synchrotron radiation photoemission techniques were used to investigate the characteristics of the Ba 4d components. Different behaviors were observed for Ba(alpha) and Ba(beta), suggesting that they originate from different layers. These findings have important implications for understanding the surface structure and properties of materials.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Iris Berg, Helen Eisenberg, Shahar Dery, Tehila Shahar, Albano Cossaro, Alberto Verdini, Luca Floreano, Tamar Stein, Elad Gross
Summary: This study investigates the correlation between adsorption geometry and nitro reduction affinity in nitroaromatics on Au surface. The results reveal that the parallel positioning of the nitro group and high surface proximity are essential descriptors for nitro reduction affinity.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Andrea Casotto, Giovanni Drera, Daniele Perilli, Sonia Freddi, Stefania Pagliara, Michele Zanotti, Luca Schio, Alberto Verdini, Luca Floreano, Cristiana Di Valentin, Luigi Sangaletti
Summary: XPS, NEXAFS, and ResPES were used to characterize a novel heterointerface between graphene and nickel phthalocyanine (NiPc) in order to identify charge transfer channels relevant to device development and operation. The results showed effective functionalization and coupling between NiPc complexes and the graphene substrate through pi-symmetry orbitals. These findings are important for potential applications in photonics, optoelectronics, and sensing.