Article
Chemistry, Multidisciplinary
Chenghui Zhu, Le Nhan Pham, Xu Yuan, Haoran Ouyang, Michelle L. Coote, Xinxing Zhang
Summary: The use of external electric fields as green and efficient catalysts in synthetic chemistry has gained significant attention. This study takes advantage of the spontaneous high electric field at the air-water interface of sprayed water microdroplets to facilitate ultrafast reactions in several halogen bond systems. The results suggest that microdroplet chemistry holds great potential for reactions facilitated by high electric fields and offers an alternative solution to the scalability problem.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Sunil Kumar Kandappa, Lakshmy Kannadi Valloli, Steffen Jockusch, Jayaraman Sivaguru
Summary: An unprecedented photochemical reactivity of 1,3-dicarbonyl compounds with amino-alkenes has been discovered, leading to the formation of dihydropyrans. This novel reaction has changed the established paradigm related to the De Mayo reaction between 1,3-dicarbonyl compounds and alkenes and allows for convenient access to the Marmycin core from commercially available reactants in a single step. Detailed origin and scope of this new photoreaction have been investigated with preliminary photophysical and mechanistic studies.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Ruben Van Lommel, Rik H. Verschueren, Wim M. De Borggraeve, Freija De Vleeschouwer, Thijs Stuyver
Summary: In this study, the authors investigated the effects of an electric field on a set of model radicals with varying complexity. They found that the electric field influenced the intrinsic philicity of the radicals, as measured by the global electrophilicity index, omega. The extent of change in philicity depended on the directionality and strength of the applied electric field, as well as the dipole moment and polarizability of the radicals.
Article
Chemistry, Multidisciplinary
Omer Kirshenboim, Alexander Frenklah, Sebastian Kozuch
Summary: The study investigated the effects of external electric fields on simple molecules near absolute zero, finding subtle but significant impacts on reaction kinetics. In addition to subtle changes in kinetics based on field strength and direction, effects such as the inversion of the Arrhenius equation, deactivation of molecular fluxionality, and system stabilization or instantaneous decomposition were also observed. These effects could be achieved with the flick of a switch.
Article
Chemistry, Physical
Tarek Scheele, Tim Neudecker
Summary: Oriented external electric fields have a strong effect on the mechanical force required to activate mechanophores, with the degree of this effect depending on the angle at which the field is applied. Mechanical force amplifies the effect of the electric field on the scissile bond of a mechanophore. Combining methods to simulate molecules in electric fields and applying mechanical force allows for an effective analysis of mechanophores in external electric fields.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Tarek Scheele, Tim Neudecker
Summary: Oriented external electric fields have a strong effect on the mechanical force required to activate mechanophores, lowering the rupture force depending on the angle of application. Mechanical force amplifies the effect of OEEFs on mechanophores.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Song Yu, Pascal Vermeeren, Trevor A. Hamlin, F. Matthias Bickelhaupt
Summary: The study demonstrates that an external electric field along the reaction axis enhances electrostatic and orbital interactions, lowering the reaction barrier. However, a field perpendicular to the reaction axis stabilizes only one stereoisomer pathway of the reaction.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Jingbai Li, Steven A. Lopez
Summary: This study uses machine-learning-accelerated photodynamics simulations to investigate the structural information and reaction outcomes of a series of fluorobenzenes. The research provides insights into the effects of pseudo Jahn-Teller distortions on the excited-state lifetimes of fluorobenzenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Physical
Kshatresh Dutta Dubey, Thijs Stuyver, Sason Shaik
Summary: This Mini-Review Article provides an overview of recent advances in the study of local electric field (LEF) governed enzyme catalysis and its application in synthetic catalyst design. The article discusses the electrostatic principles that drive enzyme catalysis and the experimental validation through vibrational Stark spectroscopy. Additionally, it highlights the role of LEFs in enzyme catalysis and explores their applications in organic synthesis and synthetic enzymes.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Physical
Tom Clarys, Thijs Stuyver, Frank De Proft, Paul Geerlings
Summary: This paper discusses the extension of the E = E[N, v] functional in a conceptual DFT context to include external electric fields for exploring chemical reactivity. Through a case study on dihalogens, the sensitivity of condensed atomic charges to polarizability is revealed, highlighting the much higher sensitivity of electronic chemical potential/electronegativity compared to chemical hardness. Symmetry breaking and stereoselectivity are shown in response functions, indicating the potential for generating enantioselectivity by exploiting differences in polarization induced by an electric field.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Alexander B. Weberg, Ryan P. Murphy, Neil C. Tomson
Summary: The power of oriented electrostatic fields (ESFs) to influence chemical bonding and reactivity has attracted growing interest. Strong ESFs have been found to contribute significantly to enzyme activity, where alignment of a substrate's changing dipole moment with a strong, local electrostatic field is responsible for enhancing the enzymatic rate. Researchers have also explored the impacts of internal electrostatic fields through the addition of ionic salts and charged functional groups, as well as externally through bulk fields between electrode plates. Incorporating charged moieties into homogeneous inorganic complexes to generate internal ESFs has great potential for novel catalyst design.
Article
Chemistry, Physical
Josep Maria Bofill, Wolfgang Quapp, Guillermo Albareda, Iberio de P. R. Moreira, Jordi Ribas-Arino
Summary: The use of oriented external electric fields (OEEF) as a tool to accelerate chemical reactions has attracted significant interest. A new model is proposed to calculate the optimal OEEF for inducing barrierless chemical reaction path. By defining an effective potential energy surface (PES) considering both the original PES and the action of a constant OEEF, the optimal OEEF can be determined by locating a special point on the PES. The geometrical aspects of the optimal bond-breaking point (optimal BBP) and the optimal OEEF are discussed using a two-dimensional model, and numerical calculations serve as proof of concept.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Organic
Dalton J. Hanaway, C. Rose Kennedy
Summary: Recent theoretical work and experiments have provided a strong conceptualization for the effects of oriented electric fields (OEFs) on organic reactions. However, evaluating reaction sensitivity to field effects has been inefficient in practice. This study presents the development of an automated tool, A.V.E.D.A, for efficient evaluation of a reaction's susceptibility to OEFs.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Wei-Wei Wang, Fu-Lin Shang, Xiang Zhao
Summary: (English Summary:)
This study explores how an oriented external electric field can modulate cycloadditions on zigzag boron nitride nanotubes to selectively control the type of reactions and products. The electric field can play opposing catalytic roles in different reactions and the effect can be easily reversed for desired outcomes.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Meilani Wibowo, Bang C. Huynh, Chi Y. Cheng, Tom J. P. Irons, Andrew M. Teale
Summary: The maximum overlap method (MOM) is used to calculate excited states by targeting non-Aufbau occupations. This method is applied to study excited states of H-3(+) and H-3 in strong magnetic fields. The changes in molecular structure under the field are examined using excited state geometry optimisations. The E-3' state is stabilized and becomes the ground state in strong fields, while the (1)A(1)' state is destabilized and its structure distorts.
Article
Chemistry, Multidisciplinary
Jiao Yu J. Wang, Mitchell T. Blyth, Michael S. Sherburn, Michelle L. Coote
Summary: This study conducted the first broad spectrum investigation into the photoenolization/Diels-Alder (PEDA) sequence, and found that substitution patterns have tolerance in the PEDA reaction, while thiocarbonyl derivatives react more slowly. The Diels-Alder reaction is predicted to have a broad scope, and CO undergoes a unique addition pathway.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Andie R. Delaney, Li-Juan Yu, Vincent Doan, Michelle L. Coote, Annie L. Colebatch
Summary: Metal-metal cooperativity is an important catalysis strategy, which requires appropriate ligand scaffolds to support close proximity of two metals. In this study, we report the nickel-promoted formation of a planar macrocyclic ligand that can support bimetallic dinickel(II) and dinickel(I) complexes. The reaction outcomes can be controlled by varying substituents and reaction conditions to favor dinucleating macrocyclic, mononucleating macrocyclic, or conventional pincer architectures.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Yichao Zhao, James Theodore Merrett, Jianwen Jin, Li-Juan Yu, Michelle Louise Coote, Philip Wai Hong Chan
Summary: This study describes a synthetic method for the alpha-alkynylation of tertiary alpha-silylamines by 1-iodoalkynes, mediated by [Au-2(mu-dppm)(2)]Cl-2 and UVA LED light (lambda = 365 nm). The reaction showed excellent functional group tolerance and could be applied to a wide range of coupling partners, as well as various bioactive molecules and natural products. Experimental and computational studies suggested an oxidative quench pathway and the involvement of a dimeric metal complex in mediating the cross-coupling of two radical species, which is unprecedented in photoredox gold catalysis.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Analytical
Mattia Belotti, Mohsen M. T. El-Tahawy, Marco Garavelli, Michelle L. Coote, K. Swaminathan Iyer, Simone Ciampi
Summary: The study develops a direct, spatiotemporally resolved optical tracking method to detect and resolve convective disturbances in electrochemical reactivity. It is found that parasitic gas evolving reactions lead to overestimates of macroscopic diffusion coefficients by 10 times. A hypothesis is proposed linking large barriers to inner-sphere redox reactions to the formation of cation-rich overscreening and crowding double layer structures in imidazolium-based ionic liquids.
ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Wanjun Xu, Shuaijun Pan, Benjamin B. Noble, Zhixing Lin, Sukhvir Kaur Bhangu, Chan-Jin Kim, Jingqu Chen, Yiyuan Han, Irene Yarovsky, Frank Caruso
Summary: This article reports on flexible metal-phenolic networks (MPNs) that exhibit stimuli-responsive behavior to various solute guests. The responsive behavior of the MPNs is primarily determined by the competitive coordination of metal ions to phenolic ligands with multiple coordination sites and solute guests. The embedding of glucose molecules into the dynamic MPNs leads to the reconfiguration of the metal-organic networks and changes in their physicochemical properties for targeted applications. This study expands the library of stimuli-responsive flexible metal-organic materials and enhances the understanding of intermolecular interactions between metal-organic materials and solute guests, which is crucial for the rational design of responsive materials for various applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Kaycee Low, Michelle L. Coote, Ekaterina I. Izgorodina
Summary: This work extends the electron deformation density-based descriptor to predict three-body interactions in trimers. The resulting Gaussian process regression (GPR) model shows good prediction accuracy on the 3B69 and S22-3 trimer data sets. A hybrid kernel function is introduced to predict the total trimer interaction energy and three-body contribution using the same descriptor. A new data set based on protein-ligand crystal structures is introduced, providing benchmark calculations for larger molecular interactions. Compared to DFT- and wavefunction-based methods, our model reduces the required SCF calculations and shows faster predictions.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Multidisciplinary
Shangxu Jiang, Yihui Xie, Yuan Xie, Li-Juan Yu, Xiaoqing Yan, Fu-Gang Zhao, Chanaka J. Mudugamuwa, Michelle L. Coote, Zhongfan Jia, Kai Zhang
Summary: This study investigates the (electro)chemical behavior of TEMPO in organic and aqueous Lewis acid electrolytes and unveils its reversible disproportionation process in aqueous media. Based on these findings, a radical polymer aqueous AIBs is designed and demonstrates promising stability and performance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jasmine M. M. Pople, Thomas P. P. Nicholls, Le Nhan Pham, Witold M. M. Bloch, Lynn S. S. Lisboa, Michael V. V. Perkins, Christopher T. T. Gibson, Michelle L. L. Coote, Zhongfan Jia, Justin M. M. Chalker
Summary: In this study, a new method for the synthesis of high sulfur content polymers was developed using electrochemically initiated ring-opening polymerization. This method offers improved safety and control of structure by eliminating the need for hazardous chemical initiators. The resulting polymer exhibits good solubility and processability. Thermal depolymerization of the polymer allows for its recycling back to the cyclic trisulfide monomer. The polymer also demonstrates effective gold sorption, suggesting potential applications in mining and electronic waste recycling.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Materials Science, Multidisciplinary
Samuel J. Tonkin, Le Nhan Pham, Jason R. Gascooke, Martin R. Johnston, Michelle L. Coote, Christopher T. Gibson, Justin M. Chalker
Summary: With increasing applications of infrared imaging, there is a demand for low-cost alternatives to traditional infrared optics materials. Sulfur-rich copolymers show promise due to their cost-effectiveness and high refractive index. This study reports on the copolymerization of cyclopentadiene with sulfur, resulting in a plastic with the highest long-wave infrared transparency observed for this class of materials. The copolymer can be used in various lens architectures and as an infrared-transparent blind for thermal imaging equipment and clandestine surveillance, suggesting broader use of sulfur copolymers in infrared optics.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Chenghui Zhu, Le Nhan Pham, Xu Yuan, Haoran Ouyang, Michelle L. Coote, Xinxing Zhang
Summary: The use of external electric fields as green and efficient catalysts in synthetic chemistry has gained significant attention. This study takes advantage of the spontaneous high electric field at the air-water interface of sprayed water microdroplets to facilitate ultrafast reactions in several halogen bond systems. The results suggest that microdroplet chemistry holds great potential for reactions facilitated by high electric fields and offers an alternative solution to the scalability problem.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Zhipeng Pei, Nicholas L. Magann, Madison J. Sowden, Rhys B. Murphy, Michael G. Gardiner, Michael S. Sherburn, Michelle L. Coote
Summary: The ground-state structure of p-QDM is typically represented as a closed shell cyclic compound, but it has been proposed to have an open shell aromatic singlet diradical form as well. Calculations reveal a 29% open-shell contribution to the structure, and dimerization occurs through a low barrier singlet diradical pathway. In contrast, TCNQ, despite having similar diradical character, shows no dimerization or reactivity with TEMPO.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Yi-Min Fan, Josemon George, Jiao Yu J. Wang, Michael G. Gardiner, Michelle L. Coote, Michael S. Sherburn
Summary: Through the study, it was found that imines can participate in intermolecular formal [4 + 2] cycloadditions with dendralenes, forming hexahydro- and octahydro-isoquinoline structures. After optimizing the conditions, the formal aza-Diels-Alder reaction proceeds with high regio- and stereoselectivity.
Review
Polymer Science
Gerard Audran, Elena G. Bagryanskaya, Raphael Bikanga, Michelle L. Coote, Olga Guselnikova, Chelsey L. Hammill, Sylvain R. A. Marque, Philippe Mellet, Pavel S. Postnikov
Summary: Dynamic Covalent Bonds (DCB) are labile covalent bonds that play a significant role in the design of next generation materials. Alkoxyamines exhibit a unique C-O DCB that can be cleaved under various stimuli, and the cleavage kinetics and thermodynamics can be controlled by modifying the structure of the molecules. Despite being easily incorporated into polymers, the dynamic covalent properties of alkoxyamines have not been fully utilized in materials sciences.
PROGRESS IN POLYMER SCIENCE
(2023)
Article
Chemistry, Organic
Ting-Ting Yuan, Jing Chen, Le Nhan Pham, Sayan Paul, Lorenzo V. White, Jialong Li, Ping Lan, Michelle L. Coote, Martin G. Banwell, Yu-Tao He
Summary: Efficient and versatile syntheses of methylene-bridged bis-heterocycles are described, which involve a visible light-mediated radical-relay sequence. This process begins with the homolysis of O-H bonds contained within & beta;,& gamma;-unsaturated oximes, generating oxygen-centred radicals that add to the tethered olefin. The resulting carbon-centered radical is then trapped by an added N-heteroarenium salt. These findings provide new insights into alkoxy radical-mediated transformations and access to new molecular scaffolds with potential applications in various settings.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Michael A. Stevens, Li Feng Lim, Le Nhan Pham, Nicholas Cox, Michelle L. Coote, Annie L. Colebatch
Summary: The reaction between the ligand 2,7-bis(6-methyl-2-pyridyl)-1,8-naphthyridine (MeL) and the MnI and MnII precursors resulted in the formation of monometallic and bimetallic manganese complexes. The EPR results showed the magnetic properties of one of the complexes.
DALTON TRANSACTIONS
(2023)