Article
Nanoscience & Nanotechnology
Zichao Wei, Kayceety Mullaj, Aleisha Price, Kecheng Wei, Qiang Luo, Srinivas Thanneeru, Shouheng Sun, Jie He
Summary: This study presents a method for preparing metal nanoparticles (NPs) using polymer N-heterocyclic carbenes (NHCs) as surface ligands. The results demonstrate that polymer NHC-modified AgNPs exhibit excellent resistance to oxidative etching and enhanced peroxidase activity.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Thibault Cauwenbergh, Nikolaos Tzouras, Thomas Scattolin, Subhrajyoti Bhandary, Andreas Simoens, Kristof Van Hecke, Christian Stevens, Steven P. Nolan
Summary: The use of weak and inexpensive bases has opened up promising perspectives for the synthesis of Au(I)-aryl complexes with valuable applications. Continuous manufacturing has proven to be a reliable partner in establishing sustainable and controlled process scalability. Via gram-scale synthesis, convenient process scalability of the developed protocol was showcased.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Physical
Annaluisa Mariconda, Marco Sirignano, Rubina Troiano, Simona Russo, Pasquale Longo
Summary: This review summarizes the research progress from 2007 to 2022 on the nucleophilic addition of amines and water to terminal and internal alkynes catalyzed by N-heterocyclic carbene gold (I/III) complexes. These reactions are environmentally sustainable and lead to important intermediates in the chemical and pharmaceutical industry.
Review
Biochemistry & Molecular Biology
Alexia Tialiou, Jiamin Chin, Bernhard K. Keppler, Michael R. Reithofer
Summary: This review summarizes the latest advances in NHCAu(I/III) complexes that interact with DNA and presents the latest research on acyclic diamino carbene gold complexes with anticancer activity, which offer additional design possibilities in targeted therapy.
Article
Chemistry, Multidisciplinary
Maxwell S. Reese, Mitchell G. Bonanno, Jamey K. Bower, Curtis E. Moore, Shiyu Zhang
Summary: This study reports the synthesis and reactivity of a series of Cu-II and Cu-III aryl complexes that closely mimic the intermediates in Cu-catalyzed C-N coupling reactions. It was found that neutral nitrogen nucleophiles can react with copper(III) aryl complexes to form C-N coupling products, but commonly observed byproducts are also generated.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Thomas Scattolin, Giovanni Tonon, Eleonora Botter, Sebastien G. Guillet, Nikolaos V. Tzouras, Steven P. Nolan
Summary: The review focuses on the design of gold-based synthons that enable the synthesis of target complexes through simple steps under mild conditions. Mechanistic aspects of their synthesis and reactivity, as well as applications as efficient pre-catalysts, antitumor agents, and photo-emissive materials, are discussed.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Laura Hippolyte, Omar Sadek, Salem Ba Sowid, Alexandre Porcheron, Nathalie Bridonneau, Sebastien Blanchard, Marine Desage-El Murr, David Gatineau, Yves Gimbert, Dimitri Mercier, Philippe Marcus, Clement Chauvier, Corinne Chaneac, Francois Ribot, Louis Fensterbank
Summary: In this paper, a straightforward synthesis method for NHC-coated gold nanoparticles (NHC-AuNPs) is reported. The commercially available gold(I) precursor is treated with an easy-to-synthesize NHC-BH3 reagent, serving as both the reducing agent and the source of surface ligands. The strategy allows efficient control over the nucleation and growth of gold particles, resulting in a wide range of particle size variation from 4.9±0.9 to 10.0±2.7 nm. The NHC-AuNPs obtained exhibit narrow size distributions, stability over months, and do not require extensive purification or size-selectivity techniques.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Runxia Nan, Yiwen Li, Zhouli Zhu, Fan Qi, Xu-Qiong Xiao
Summary: This study focused on the synthesis and transformation of functional groups in metallacarboranes, and investigated their impact on the structure and properties of the metallacarborane framework.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yuto Kondo, Hiroyuki Kimura, Minon Sasaki, Sumina Koike, Yusuke Yagi, Yasunao Hattori, Hidekazu Kawashima, Hiroyuki Yasui
Summary: Direct radioiodination of peptides using copper-mediated iododeboronation is a promising method to solve issues with classical direct radiolabeling. However, the optimization of reaction conditions for different peptides is not fully understood, especially regarding the effects of water-containing solvents on labeling efficiency. This study investigates the effect of water on copper-mediated radioiododeboronation and identifies key factors for successful radiolabeling in water-organic solvents. The findings contribute to improving the design of boronic peptide precursors and copper-mediated iododeboronation protocols.
Article
Chemistry, Multidisciplinary
Alexander S. Mikherdov, Mingoo Jin, Hajime Ito
Summary: In this study, it was demonstrated experimentally that Au(i) metal center can form predictable halogen bonding interactions with neutral Au(i) complexes. The nature of these interactions was elucidated through various experimental and computational techniques, revealing a connection between the structure and properties of the metal center as XB acceptors.
Article
Chemistry, Multidisciplinary
Lenka Pallova, Laura Abella, Marion Jean, Nicolas Vanthuyne, Cecile Barthes, Laure Vendier, Jochen Autschbach, Jeanne Crassous, Stephanie Bastin, Vincent Cesar
Summary: The first efficient chiral helicene-NHC gold(I) complexes for enantioselective catalysis have been synthesized. Their structural and stereochemical characterization confirms their potential in asymmetric catalysis, demonstrated by the benchmark cycloisomerization reaction with high enantiomeric excess.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Biochemistry & Molecular Biology
Iogann Tolbatov, Tiziano Marzo, Cecilia Coletti, Diego La Mendola, Loriano Storchi, Nazzareno Re, Alessandro Marrone
Summary: The study investigated the reactivity of antitumor metal complexes with protein binding sites cysteine and selenocysteine, revealing a higher affinity towards the deprotonated forms. The neutral forms' binding process was found to be slow, while protonation from an external source was required for the deprotonated forms. The reactivity of all coinage metals towards cysteine and selenocysteine was similar, with Au(I) complex exhibiting higher reaction and activation free energies compared to Cu(I) and Ag(I).
JOURNAL OF INORGANIC BIOCHEMISTRY
(2021)
Article
Chemistry, Physical
Hua Zhang, Ting Xu, Dongdong Li, Tao Cheng, Jing Chen, Yang Zhou
Summary: A novel series of bis Indy-NHC gold complexes were developed and investigated via a mild Agcarbene transfer route. The catalytic properties of these complexes, especially gold complex E1, showed high catalytic activity in the oxidation of various benzylic substrates with excellent yields using TBHP as oxidant.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Biochemistry & Molecular Biology
Stefano Scoditti, Francesco Chiodo, Gloria Mazzone, Sebastien Richeter, Emilia Sicilia
Summary: The photophysical properties of two classes of porphyrins and metalloporphyrins linked to N-heterocyclic carbene (NHC) Au(I) complexes were investigated for their potential application in photodynamic therapy. Results showed that these compounds possess appropriate properties for generating cytotoxic singlet molecular oxygen and can be used as photosensitizers. The heavy atom effect in promoting the intersystem crossing process was found to vary depending on the identity and position of the metal center in the porphyrin core or linked to the peripheral NHC.
Review
Chemistry, Inorganic & Nuclear
Sophie R. Thomas, Angela Casini
Summary: The unique properties and high synthetic flexibility of N-heterocyclic carbenes make them attractive tools for developing new nanomaterials and studying their properties. This review focuses on NHC-stabilized gold nanoparticles with potential for biological applications, aiming to present an overview of the strategies adopted to achieve water-soluble biocompatible nanoparticles. The combinatorial design of NHC ligand shell functionality presents new perspectives for this relatively unexplored research area.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Tao Wang, Abhishek Kumar Gupta, Sen Wu, Alexandra M. Z. Slawin, Eli Zysman-Colman
Summary: We discovered a general design principle for materials that exhibit multiple room-temperature phosphorescence (RTP) processes. By modulating the hybridization between donor and acceptor groups, we achieved multiple RTP processes in sp3 C-linked donor-acceptor compounds. However, in sp2 C-linked counterparts, only one locally excited triplet state phosphorescence was observed due to enhanced excitonic coupling. Our findings provide insights into the dynamics of higher-lying triplet excited states and offer a fundamental design principle for compounds with multiple RTP.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Angeliki Giannoulis, Katrin Ackermann, Alexey Bogdanov, David B. B. Cordes, Catherine Higgins, Joshua Ward, Alexandra M. Z. Slawin, James E. E. Taylor, Bela E. E. Bode
Summary: Nitroxides, a unique class of persistent radicals, have a wide range of applications, from spin probes to polarizing agents. This study focuses on the synthesis of pyrroline-based nitroxide radicals and compares two possible synthetic routes for forming two key intermediates. The synthesized compounds were characterized using X-ray crystallography and their electronic communication was quantified using Continuous Wave Electron Paramagnetic Resonance (CW-EPR). This research expands the repertoire of mono- and bis-nitroxides and paves the way for studying quantum coherence effects and using them as polarizing agents.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Min Xu, Chencheng Liu, Aaron B. Naden, Herbert Fruechtl, Michael Buehl, John T. S. Irvine
Summary: The in situ formation of bi-metallic nanoparticles on B-site co-doped perovskite fibers is investigated. These fibers exhibit a high degree of exsolution, with NiCo or Ni3Fe bi-metallic nanoparticles with average diameters of 29 nm and 35 nm respectively. These perovskite fibers are used as cathode materials in pure CO2 electrolysis cells and show improved performance after in situ electrochemical switching.
Article
Nanoscience & Nanotechnology
Pagidi Sudhakar, Suman Kuila, Kleitos Stavrou, Andrew Danos, Alexandra M. Z. Slawin, Andrew Monkman, Eli Zysman-Colman
Summary: Extensive research has been conducted to develop thermally activated delayed fluorescence (TADF) emitters with pure-blue emission. In this study, a novel weak donor, 1,4-azaborine (AZB), was synthesized and combined with a triazine acceptor to create high-performance TADF emitters. The results showed that the AZB-Ph-TRZ emitter had a photoluminescence quantum yield (phi(PL)) of 27% and emitted at 415 nm, while the shortened analogue AZB-TRZ exhibited red-shifted emission and fast reverse intersystem crossing. These findings expand the toolkit for designing blue TADF materials in the future.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Subeesh Madayanad Suresh, Le Zhang, Tomas Matulaitis, David Hall, Changfeng Si, Gaetano Ricci, Alexandra M. Z. Slawin, Stuart Warriner, David Beljonne, Yoann Olivier, Ifor D. W. Samuel, Eli Zysman-Colman
Summary: Two multiresonant thermally activated delayed fluorescence (MR-TADF) emitters are demonstrated. The borylation of a deep-blue MR-TADF emitter, DIDOBNA-N, results in a new near-UV MR-TADF emitter, MesB-DIDOBNA-N, with a blueshifted and narrowed emission. DIDOBNA-N emits bright blue light with high efficiency, while the OLED based on MesB-DIDOBNA-N shows the highest efficiency and the bluest emission among MR-TADF OLEDs reported to date.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Physical
Lin-jie Yang, Wenye Xuan, David Webster, Lethy Krishnan Jagadamma, Teng Li, David N. Miller, David B. Cordes, Alexandra M. Z. Slawin, Graham A. Turnbull, Ifor D. W. Samuel, Hsin-Yi Tiffany Chen, Philip Lightfoot, Matthew S. Dyer, Julia L. Payne
Summary: One of the advantages of organic-inorganic metal halides is their highly tuneable structures and properties, which are important for optimizing materials for photovoltaics and optoelectronic devices. In this study, bromine was included in a layered perovskite to induce a decrease in band gap and a structural transition. The inclusion of bromine also resulted in the formation of a new band in the electronic structure and a significant increase in mobility and/or carrier concentration. This work highlights the potential of molecular inclusion as a tool to tune the electronic properties of layered organic-inorganic perovskites.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Eimantas Duda, Subeesh Madayanad Suresh, David Hall, Sergey Bagnich, Rishabh Saxena, David B. Cordes, Alexandra M. Z. Slawin, David Beljonne, Yoann Olivier, Anna Koehler, Eli Zysman-Colman
Summary: This study introduces a molecular design that gradually increases the number of quasi-degenerate states to enhance the efficiency of thermally activated delayed fluorescence (TADF) using the oligomer approach. By selecting and arranging benzonitrile (BN) acceptors and amine donors, connected together via repetitive donor-acceptor units, the number of quasi-degenerate states is gradually increased. It is found that increasing the size of the oligomer enhances the rates of intersystem crossing and reverse intersystem crossing.
CHEMISTRY OF MATERIALS
(2023)
Editorial Material
Chemistry, Multidisciplinary
Paul Zaby, Jan Blasius, Anna K. K. Mueller, Steven P. P. Nolan, Oldamur Holloczki
Summary: In this issue, Oldamur Hollczki and co-workers from the Universities of Bonn, Ghent and Debrecen are featured on the cover. The image showcases the quest for an ionic base that can combine with the acidic proton of an imidazolium cation to form a carbene complex. For the full article, visit 10.1002/chem.202203636.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Sebastien G. Guillet, Ishfaq Ibni Hashim, Marek Belis, Kristof Van Hecke, Catherine S. J. Cazin, Steven. P. Nolan
Summary: A simple synthetic method for synthesizing various [Rh(acac)(CO)(NHC)] complexes is presented. In situ infrared monitoring provides valuable information on the reaction mechanism, including the identification of a crucial intermediate. Understanding the reaction mechanism has led to the discovery of novel pathways to commonly used congeners.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Materials Science, Multidisciplinary
Tao Wang, Abhishek Kumar Gupta, David B. Cordes, Alexandra M. Z. Slawin, Eli Zysman-Colman
Summary: This study reports the observation of emission directly from the T-2 state in multi-resonant thermally activated delayed fluorescence (MR-TADF) emitters for the first time by modulating the conjugation between the emissive center and donor substituent. Theoretical and photophysical investigations reveal that the Delta E-S1T2 difference influences the reverse intersystem crossing rate. Therefore, designing MR-TADF emitters with degenerate S-1 and T-2 states provides a possible solution to mitigate device efficiency roll-off.
ADVANCED OPTICAL MATERIALS
(2023)
Review
Chemistry, Multidisciplinary
Thomas Scattolin, Giovanni Tonon, Eleonora Botter, Sebastien G. Guillet, Nikolaos V. Tzouras, Steven P. Nolan
Summary: The review focuses on the design of gold-based synthons that enable the synthesis of target complexes through simple steps under mild conditions. Mechanistic aspects of their synthesis and reactivity, as well as applications as efficient pre-catalysts, antitumor agents, and photo-emissive materials, are discussed.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Lutao Zhang, Francesca A. Christie, Anna E. Tarcza, Helena G. Lancaster, Laurence J. Taylor, Michael Buhl, Olga L. Malkina, J. Derek Woollins, Cameron L. Carpenter-Warren, David B. Cordes, Alexandra M. Z. Slawin, Brian A. Chalmers, Petr Kilian
Summary: A series of peri-substituted acenaphthene-based phosphine selenoether bidentate ligands were synthesized and their properties in coordination with metals were investigated. The rigid ligands exhibited strong coupling effects and the coordination atoms were bridged by Lewis acidic motifs in the solid-state structures. Analysis of the NMR and X-ray diffraction data of the synthesized metal complexes provided insights into the interaction between the ligands and metals.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Daniel J. Davidson, Fei Lu, Laura Faas, Daniel M. Dawson, Geoffrey P. Warren, Isabella Panovic, James R. D. Montgomery, Xiaoyan Ma, Boris G. Bosilkov, Alexandra M. Z. Slawin, Tomas Lebl, Afroditi Chatzifragkou, Steve Robinson, Sharon E. Ashbrook, Liz J. Shaw, Smilja Lambert, Isabella Van Damme, Leonardo D. Gomez, Dimitris Charalampopoulos, Nicholas J. Westwood
Summary: Cocoa pod husks, an underutilized resource in chocolate manufacturing, contain lignin with potential applications. An optimized extraction method led to high-quality lignin, allowing for further investigation of its structure and chemical transformation abilities. Preliminary analysis of other product streams from the husks was also conducted.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Inorganic & Nuclear
Vladislav A. Voloshkin, Yaxu Liu, Marek Belis, Min Peng, Kristof Van Hecke, Catherine S. J. Cazin, Steven P. Nolan
Summary: The synthesis of novel phosphine palladium PEPPSI and dimer complexes bearing RuPhos, SPhos and XPhos phosphines is reported. The crystal structures of XPhos Pd PEPPSI with pyridine, SPhos Pd PEPPSI with 3-chloropyridine as throw-away ligands and the RuPhos palladium dimer were obtained and compared with previously reported congeners. The catalytic activity of these complexes was examined via a C-N coupling reaction, and it was found that RuPhos complex 2b showed the highest catalytic activity with 97% yield at a low catalyst loading. The addition of 3-pentanone significantly improved the yields of phosphine dimers and PEPPSI complexes when the reactions were performed in THF.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Benon Maliszewski, Eleonora Casillo, Perrine Lambert, Fady Nahra, Catherine Cazin, Steven Nolan
Summary: This article reports an efficient olefin hydrosilylation protocol using Pt(ii)-thioether-based pre-catalysts. These simple and readily available complexes exhibit excellent catalytic performance and offer significant advantages over existing alternatives, enabling rapid and high conversions at ppm-level catalyst loadings.
CHEMICAL COMMUNICATIONS
(2023)
