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)
Review
Chemistry, Multidisciplinary
Hayoung Song, Ewa Pietrasiak, Eunsung Lee
Summary: This Account describes the recent work on developing NHC-derived persistent radicals and their prospective applications. NHCs not only stabilize radicals but also interact reversibly with gas molecules. In medicine-related applications, NHC-NO radicals can serve as a platform for NO release in tumor treatment. In energy storage materials, NHC-supported radicals can be used as cathode active materials in batteries. Moreover, stable organic radicals derived from NHCs have potential applications in flexible devices and MRI contrasting agents.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Xiaoye Yu, Anirban Maity, Armido Studer
Summary: An alternative disconnection approach using aroyl fluorides as bifunctional reagents for fluoroaroylation of gem-difluoroalkenes through cooperative photoredox and N-heterocyclic carbene (NHC) catalysis is reported. This strategy enables the synthesis of alpha-CF3-substituted ketones efficiently and without the use of expensive or sensitive reagents and the requirement for ketone pre-functionalization. The methodology also allows rapid access to mono- or difluoroalkyl ketones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xin Li, Yi-Lin Wang, Can Chen, Ying-Feng Han
Summary: In this study, a series of carbene-triphenylamine hybrids with tunable emission were synthesized. These hybrids can be converted to carbon-centered luminescent radicals with blue-to-cyan emissions or nitrogen-centered luminescent radicals with orange emissions through chemical reduction or oxidation, respectively. The nitrogen-centered radicals exhibited good stability in atmospheric air.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Michael S. M. Philipp, Mirjam J. Krahfuss, Krzysztof Radacki, Udo Radius
Summary: A systematic study on Lewis-acid/base adducts of N-heterocyclic carbenes and cyclic (alkyl)(amino)carbene with antimony(III) chlorides was conducted, revealing a series of products formation and thermal isomerization reactions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Le Dung Pham, Red O. Smith-Sweetser, Briana Krupinsky, Carolyn E. Dewey, Jessica R. Lamb
Summary: This study demonstrates that NHC-CDI adducts can be used as masked precursors for switchable organocatalysis, and the CDI substituents can control the reaction profile without changing the NHC structure. By controlling the electronic variations and perturbations on the CDI, the catalytically active temperature and catalyst release range can be controlled.
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
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
Carmela De Risi, Arianna Brandolese, Graziano Di Carmine, Daniele Ragno, Alessandro Massi, Olga Bortolini
Summary: Oxidative N-heterocyclic carbene (NHC) catalysis has the potential to achieve oxidative and oxygenative transformations, generating various NHC-bound intermediates and enabling non-umpolung processes through the activation of carbon atoms and heteroatoms. This review aims to discuss the recent developments in the field of oxidative NHC catalysis since 2014, with a focus on pivotal intermediates and their mechanistic involvement. More details can be found in the review article by C. De Risi and co-workers.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Carmela De Risi, Arianna Brandolese, Graziano Di Carmine, Daniele Ragno, Alessandro Massi, Olga Bortolini
Summary: Oxidative N-heterocyclic carbene (NHC) catalysis enables oxidative and oxygenative transformations, producing various NHC-bound intermediates and facilitating non-umpolung processes by activating carbon atoms and heteroatoms. This review discusses the developments in the literature on oxidative NHC catalysis since 2014, with a specific focus on pivotal intermediates and their mechanistic involvement.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Iris Berg, Einav Amit, Lillian Hale, F. Dean Toste, Elad Gross
Summary: In this study, a N-heterocyclic carbene (NHC) nanolayer was successfully anchored on the surface of a copper electrode using an electrochemical method, resulting in improved oxidation resistance of copper.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Physical
Sourav Sekhar Bera, Michal Szostak
Summary: This comprehensive review presents catalytic methods utilizing cobalt-NHC complexes, focusing on catalyst structure, the role of the NHC ligand, properties of the catalytic system, mechanism, and synthetic utility. The survey suggests that well-defined cobalt-NHC catalysts have great potential in the design and application of catalytic reactions using more abundant 3d transition metals.
Article
Chemistry, Multidisciplinary
Hyunho Kim, Minseop Kim, Hayoung Song, Eunsung Lee
Summary: The synthesis of ambiphilic N-heterocyclic carbene ligand indol-2-ylidene (IdY, A) was described, along with its ambiphilicity and synthetic utility. Experimental and computational studies showed that IdY lies between CAAC-5 and CAArC, with copper complexes capable of carboboration of terminal alkynes with high regioselectivity and good yields within 30 minutes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Mirjam J. Krahfuss, Radius Udo
Summary: The reactivity of the N-heterocyclic silylene Dipp(2)NHSi towards various Lewis acids, halides and other compounds was investigated, resulting in the formation of specific adducts and insertion products. However, frustrated Lewis pair reactivity was not observed in the tested adducts, indicating potential limitations of their small organic molecule activation abilities.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Review
Chemistry, Inorganic & Nuclear
Hui Shen, Guolong Tian, Zhen Xu, Lingzheng Wang, Qingyuan Wu, Yuhao Zhang, Boon K. Teo, Nanfeng Zheng
Summary: This review provides an overview of the recent research advances in the use of N-heterocyclic carbenes (NHCs) as stabilizing agents and functionality modifiers for metal nanoparticles (NPs) and nanoclusters (NCs). It discusses the development of effective strategies for decorating metal NPs with NHCs and the improvements in catalytic performances achieved through NHC ligation on heterogeneous metal nanocatalysts. The review also highlights the synthesis of atomically precise NHC-stabilized metal NCs and their crystallographic structure analysis, which contribute to a better understanding of the carbene-metal interface at the atomic level. The review concludes with personal perspectives on the future development of this promising field.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Nanoscience & Nanotechnology
Graham Leverick, Shuting Feng, Pedro Acosta, Samuel Acquaviva, Fanny Barde, Stephane Cotte, Yang Shao-Horn
Summary: Li-O-2 batteries have higher gravimetric energy density than Li-ion batteries, but their practical use is limited by issues with oxidizing discharge products. This study demonstrates that interhalide redox mediators based on LiI/LiBr and LiI/LiCl mixtures can increase O-2 evolution and reduce charging potential and CO2 evolution in Li-O-2 batteries.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Multidisciplinary Sciences
Tian Xie, Arthur France-Lanord, Yanming Wang, Jeffrey Lopez, Michael A. Stolberg, Megan Hill, Graham Michael Leverick, Rafael Gomez-Bombarelli, Jeremiah A. Johnson, Yang Shao-Horn, Jeffrey C. Grossman
Summary: This paper presents a method to accelerate the screening of polymer electrolytes using a multi-task graph neural network. It achieves accurate predictions of multiple properties and explores a larger space while providing an open dataset.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Teruhiko Saito, Megan R. Hill, Shao-Xiong Lennon Luo, Hong-Zhou Ye, Troy Van Voorhis, Jeremiah A. Johnson
Summary: A catalytic method for converting common unsaturated polymers into poly(acetylene)-based multiblock copolymers suitable for electronics applications is presented. This method can also be applied to the conversion of polyethylene into PA-containing multiblock materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Runze Liu, Zehao Sun, Hejin Huang, Jeremiah A. Johnson, Alfredo Alexander-Katz, Caroline A. Ross
Summary: Diblock Janus-type A-branch-B bottlebrush copolymers (di-JBBCPs) consist of a backbone with alternating A and B side chains, allowing for microphase separation perpendicular to the backbone. The self-assembly of di-JBBCPs was theoretically investigated using a reparametrized dissipative particle dynamics (DPD) model, and the results were compared with experimental data. The model showed good correspondence with the experimentally observed cylinder, gyroid, and lamellar morphologies, and predicted additional spherical phases, indicating the diversity of morphologies achievable with complex BCP molecular architectures.
Article
Chemistry, Multidisciplinary
Keith E. L. Husted, Abraham Herzog-Arbeitman, Denise Kleinschmidt, Wenxu Zhang, Zehao Sun, Alyssa J. Fielitz, An N. Le, Mingjiang Zhong, Jeremiah A. Johnson
Summary: Graft copolymers provide a versatile platform for designing self-assembling materials, but controlling their thermomechanical and morphological properties has been challenging. In this study, a strategy for controlling these properties by varying pendant groups was discovered. This strategy allows for the design of a wide range of materials with different properties. The study also simplifies graft copolymer synthesis and provides access to a diverse family of silicone-based materials.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Gabriel Bradford, Jeffrey Lopez, Jurgis Ruza, Michael A. Stolberg, Richard Osterude, Jeremiah A. Johnson, Rafael Gomez-Bombarelli, Yang Shao-Horn
Summary: Solid polymer electrolytes (SPEs) have the potential to improve lithium-ion batteries by enhancing safety and enabling higher energy densities. A chemistry-informed machine learning model was developed to predict ionic conductivity of SPEs, using data from hundreds of experimental publications. The model encodes the Arrhenius equation into the readout layer of a neural network and has improved accuracy in predicting ionic conductivity.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Physical
Matthew A. Pearson, Sachin Bhagchandani, Mircea Dinca, Jeremiah A. Johnson
Summary: A strategy of mixing multivalent polymer ligands with MOF-forming linkers and free linkers is investigated to alter the degree of polymer incorporation in polyMOFs and tune their properties, resulting in polyMOFs with superior N-2 and CO2 uptake. The mixed ligand approach is further extended to create multivariate (MTV)-polyMOFs without the addition of small molecule components.
MOLECULAR SYSTEMS DESIGN & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Herbert Wakefield, Ilia Kevlishvili, Kelsie E. Wentz, Yunxin Yao, Tatiana B. Kouznetsova, Sophia J. Melvin, Em G. Ambrosius, Abraham Herzog-Arbeitman, Maxime A. Siegler, Jeremiah A. Johnson, Stephen L. Craig, Heather J. Kulik, Rebekka S. Klausen
Summary: The cis- and trans-isomers of a silacycloheptene were selectively synthesized using a silyl dianion, providing a novel method for studying strained cycloalkenes. Quantum chemical calculations and crystallographic signatures confirmed that the trans-isomer is more strained than the cis isomer. The trans-isomer also exhibited unique reactivity in ring-opening metathesis polymerization (ROMP) and showed increased molecular compliance compared to carbon-based analogues.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Haley K. Beech, Jeremiah A. Johnson, Bradley D. Olsen
Summary: Small angle neutron scattering was used to measure the single chain radii of gyration of end-linked polymer gels before and after cross-linking. The prestrain, which is the ratio of the average chain size in a cross-linked network to that of a free chain in solution, increased as gel synthesis concentration decreased near the overlap concentration. Dilute gels with higher loop fractions were found to be spatially homogeneous. The results provide a reference for network theories that rely on prestrain for the calculation of mechanical properties.
Article
Chemistry, Multidisciplinary
Alayna M. Johnson, Jeremiah A. Johnson
Summary: Bifunctional silyl ether (BSE)-containing high-density polyethylene (HDPE)-like materials have been synthesized under mild polymerization and hydrogenation conditions. Both the concentration of BSEs in the polymer chain and the silicon steric bulk can be tuned to yield materials with HDPE-like thermomechanical properties. The materials undergo two distinct deconstruction pathways and can be recycled without compromising their mechanical strength.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Michael A. Stolberg, Benjamin A. Paren, Pablo A. Leon, Christopher M. Brown, Gavin Winter, Kiarash Gordiz, Alberto Concellon, Rafael Gomez-Bombarelli, Yang Shao-Horn, Jeremiah A. Johnson
Summary: Solid polymer electrolytes have the potential to enable safer and more energy-dense batteries. This study investigates the impact of anion dissociation energy on ion conduction in solid polymer electrolytes. The researchers developed ionenes with various cations and found that the addition of a cation-coordinating solvent greatly enhanced ionic conductivity without disrupting the lamellar structure. This work demonstrates that molecular design can facilitate significant improvements in ion conduction in solid polymer electrolytes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Tetsu Ouchi, Wencong Wang, Brooke E. E. Silverstein, Jeremiah A. A. Johnson, Stephen L. L. Craig
Summary: The influence of strand length on deformation and tension in a polymer network was studied using mechanophore force probes. It was found that the critical strain at which measurable mechanochromism is observed is correlated with the strain hardening of the matrix, but independent of the molecular length of the probes. The rate of decoloration during relaxation of the network was found to depend on the relaxing strain, indicating the effect of residual tension on the reversion reaction.
Article
Chemistry, Multidisciplinary
Keith E. L. Husted, Abraham Herzog-Arbeitman, Denise Kleinschmidt, Wenxu Zhang, Zehao Sun, Alyssa J. Fielitz, An N. Le, Mingjiang Zhong, Jeremiah A. Johnson
Summary: Based on experimental results from a library of 92 polynorbornene-graft-polydimethylsiloxane (PDMS) copolymers, a versatile backbone-pendant sequence-control strategy is discovered, which provides a simple method for precisely controlling the thermomechanical and morphological properties of graft copolymers. Small structural variations of pendant groups in small-molecule comonomers have significant impacts on various properties of silicone-based graft copolymers, resulting in a wide range of designable materials properties. This study reveals a new pendant-group-mediated self-assembly strategy that simplifies graft copolymer synthesis and enables the development of a diverse family of silicone-based materials with tailored performance specifications.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Organic
Landon J. Kilgallon, Yang Shao-Horn, Jeremiah A. Johnson
Summary: A simple and scalable method for synthesizing DMTMSA and other trifluoromethanesulfonamide solvents is described. No specialized glassware is needed, and water is used as the solvent with an ice bath for cooling. The optimized process is highly efficient and reduces waste.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Alayna M. Johnson, Keith E. L. Husted, Landon J. Kilgallon, Jeremiah A. Johnson
Summary: A new class of deconstructable polysilylethers was synthesized via entropy-driven ring-opening metathesis polymerization (ED-ROMP). These polymers exhibit good thermal stability and ultra-low T-g. They can be rapidly deconstructed by cleaving the silicon-oxygen linkages and partially depolymerized with the addition of exogenous metathesis catalyst.
CHEMICAL COMMUNICATIONS
(2022)
