Review
Crystallography
Niall J. English
Summary: This article discusses the impact of externally applied electric fields on the properties of crystals, focusing on the role of thermodynamic and kinetic processes in crystals and providing a framework for predictive molecular design to enhance understanding of field crystals.
Review
Crystallography
Niall J. English
Summary: Elucidating the mechanisms of molecular solidification in both homo- and heterogeneous systems, especially the effect of external applied fields like electric fields, is crucial for understanding natural phenomena, conducting state-of-the-art experiments, and optimizing industrial processes.
Article
Chemistry, Multidisciplinary
Paul Geerlings, Frank De Proft
Summary: The necessity of incorporating new external variables in the context of conceptual DFT (CDFT) is discussed. Electric and magnetic fields, mechanical forces, and confinement are proposed as valuable new variables. The study shows that these new variables are important for understanding chemical phenomena under different conditions.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Review
Chemistry, Physical
Shiyue Wu, Xiaoqing Yang, Heng Jing, Yue Chu, Jianping Yuan, Zhanxia Zhu, Kama Huang
Summary: In this study, the effect of external electric fields on the interaction between sulfur dioxide and water was investigated using density functional theory (DFT) and molecular dynamics (MD) methods. The results showed that the electric field reduces the binding energy between sulfur dioxide and water, inhibits the diffusion of sulfur dioxide, and decreases its solubility.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
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
Xiangyu Ge, Xiaodong Wu, Qiuyu Shi, Wenzhong Wang
Summary: This study investigated the lubrication performances of polyalkylene glycols, which are insulating oils, under external electric fields. The results showed that these electric fields significantly influenced the lubrication performances and there was an optimal voltage for friction reduction improvement. Surface analysis and experimental results indicated that the formation of adsorption film and the reduction of certain substances contributed to improved friction performance under negative voltage conditions. This work demonstrated the impact of external electric fields on the lubrication performances of insulating oils and proposed a lubrication model for understanding the lubrication mechanisms in electric environments.
Article
Chemistry, Physical
Xin He, Ben-Xi Zhang, Shuo-Lin Wang, Yi-Feng Wang, Yan-Ru Yang, Xiao-Dong Wang, Duu-Jong Lee
Summary: This study used molecular dynamic simulations to investigate the coalescence dynamics of two charged droplets under three types of electric fields. It found that the contact time is shortest under the DC electric field, followed by the AC and pulsed DC electric fields. The critical field strengths of DC and AC electric fields are the same but lower than that of the pulsed DC electric field.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Chemistry, Physical
ShiQuan Wu, LiMin Lu, Li Li, Bin Shi, TianYu Tang, XianHao Zhao, XiaoNan Wei, YanLin Tang
Summary: In this study, the effects of applied electric fields on the geometric structure, energy, dipole moment, and molecular infrared spectrum of Dicycloheptarubicene (DHR) were investigated. The results showed that the applied electric field can change the electron excitation characteristics and excitation types of DHR molecules, as well as the hole transfer rate. This provides a theoretical basis for designing DHR molecules as organic semiconductors in the future.
COMPUTATIONAL AND THEORETICAL CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Yaolong Zhang, Bin Jiang
Summary: This study proposes a universal field-induced recursively embedded atom neural network (FIREANN) model that incorporates the effects of external fields on chemical structure and reactivity into machine learning models, demonstrating its potential for efficient first-principles modeling of complicated systems.
NATURE COMMUNICATIONS
(2023)
Article
Physics, Condensed Matter
M. Mirzaei, T. Vazifehshenas, T. Salavati-fard, B. Tanatar
Summary: We investigate the dynamic optical transition of monolayer silicene in the presence of external electric and exchange fields. Our study shows that the external fields break the spin and valley degeneracies of silicene, and the longitudinal optical response is strongly dependent on the exchange field. Additionally, we find that the dominant spin subband in the response to polarized light can change depending on the type of incident light polarization.
JOURNAL OF PHYSICS-CONDENSED MATTER
(2022)
Article
Polymer Science
Alina Wettstein, Diddo Diddens, Andreas Heuer
Summary: This study investigates the effects of an external electric field on poly(ethylene oxide) (PEO) doped with lithium-bis-(trifluoromethane)sulfonimide (LiTFSI) salt through extensive atomistic molecular dynamics simulations. The research reveals a transformation in the structure of PEO chains and nonlinear behavior in dynamic properties under the influence of the electric field. Surprisingly, the study shows a slowdown in ion transport instead of enhancement due to structural changes induced by the field application.
Article
Chemistry, Physical
Nuerbiye Aizezi, Jingyan Zheng, Kelaiti Xiao, Mei Xiang, Bumaliya Abulimiti, Aidehaierjiang Manapu
Summary: This study investigates the dissociation properties of sulfuryl fluoride (SO2F2) under external electric fields (EEFs) using computational methods. The results show that increasing the electric field intensity leads to elongation of bonds, decrease in total energy, decrease in energy gap, and significant red shift in infrared spectrum.
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS
(2022)
Article
Nanoscience & Nanotechnology
Mahboubeh Kargar, Amir Lohrasebi
Summary: The study found that the application of external electric fields affects the dynamics of water droplets confined between different surfaces, potentially leading to additional pressure on the surfaces. This induced pressure may affect the lifespan of multilayer nano-filters.
JOURNAL OF NANO RESEARCH
(2021)
Article
Chemistry, Physical
Xiangqian Wang, Haiyan Wang, Lifeng Zheng, Chun Zhu, Jin-Xia Liang
Summary: The study systematically investigates Mn-corrolazine-catalyzed CH(4)oxidation and the regulation of its oriented external electric fields using first-principle calculations. The results show that when an external electric field is applied, the reactant and transition state of the oxidation reaction are stabilized, leading to a decrease in activation energy.
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Hooman Hadidi, Reza Kamali
Summary: In this study, non-equilibrium molecular dynamics simulations were used to investigate the effects of external electric fields on the gating mechanism and water permeability of human aquaporin-2 (AQP2). The results showed that different directions of the electric field can lead to varied conformations of the selectivity filter region in AQP2, affecting water molecule translocation and permeability.
JOURNAL OF BIOMOLECULAR STRUCTURE & DYNAMICS
(2022)
Article
Chemistry, Organic
Croix J. Laconsay, Tyler C. Rho, Dean J. Tantillo
Summary: In this study, the hyperconjugation/conjugation through-bond stereoelectronic effects in 3-azabicyclo[3.3.1]nonanes were investigated using density functional theory to explain the puzzling differences in reactivity between a vinylogous chloride and a vinylogous ester.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Sarah N. Dishman, Croix J. Laconsay, James C. Fettinger, Dean J. Tantillo, Jared T. Shaw
Summary: Intramolecular C-H insertions with donor/donor dirhodium carbenes provide a concise and highly stereoselective method to set two contiguous stereocenters in a single step. The study demonstrates that donor/donor carbenes undergo uniquely stereoselective reactions that originate from a stepwise reaction mechanism, in contrast to the analogous concerted reactions of carbenes with one or more electron-withdrawing groups attached.
Article
Chemistry, Organic
Jin Liang, Amy T. Merrill, Croix J. Laconsay, Anwei Hou, Qingyu Pu, Jeroen S. Dickschat, Dean J. Tantillo, Qiang Wang, Reuben J. Peters
Summary: A barley diterpene synthase (HvKSL4) was found to produce (14S)-cleistantha-8,12-diene (1). The formation of this compound involves a series of complex rearrangements, which were elucidated through quantum chemical calculations and labeling studies.
Article
Chemistry, Organic
Qinxuan Wang, Jiun-Le Shih, Ka Yi Tsui, Croix J. Laconsay, Dean J. Tantillo, Jeremy A. May
Summary: This study investigated various types of Huisgen cyclization or nitrene/carbene alkyne cascade reactions with different types of termination. Accessible nitrene precursors were evaluated, and carbonazidates were found to be the only effective initiators. The reaction outcome can be influenced by solvents, terminal alkynyl substituents, and catalysts. The mechanism was studied both computationally (using density functional theory) and experimentally, revealing relevant intermediates and plausible reaction pathways.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Croix J. Laconsay, Dean J. Tantillo
Summary: We study the escape channels of dirhodium carbene intermediates from cycloheptatrienyl diazo compounds using density functional theory. In principle, intramolecular cyclopropanation could provide a novel pathway to semibullvalenes (SBVs). Our analysis of the potential energy surface reveals that methylating carbon-7 can suppress a competing β-hydride migration pathway, increasing the likelihood of SBV formation. Additionally, we discover unusual spirononatriene, spironorcaradiene, and metal-stabilized 9-barbaralyl cation structures as local minima during our explorations.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Priyank Kumar Sharma, Akanksha Babbar, Dibyendu Mallick, Soumyajit Das
Summary: In this study, a nonbenzenoid isomeric counterpart, 1-ethoxyphenanthro[9,10e]acephenanthrylene 8, was synthesized and converted to an azulene-embedded motif 9. Aromaticity and single-crystal analyses revealed a formal azulene core for 9, which exhibited a smaller HOMO-LUMO energy gap, charge-transfer absorption band, and brighter fluorescence compared to 8. The reduction potentials of 8 and 9 were nearly identical, and DFT calculations supported these observations.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Priyank Kumar Sharma, Dibyendu Mallick, Himanshu Sharma, Soumyajit Das
Summary: In this study, Dicyclopenta[c]fluorenothiophene 5 was synthesized as an isoelectronic polycyclic heteroarene analogue. Experimental analysis and theoretical calculations showed that 5 exhibited a quinoidal ground state with a degree of antiaromaticity higher than sindacenodifluorene 3.
Article
Chemistry, Multidisciplinary
Sudip Baguli, Subham Sarkar, Soumajit Nath, Dibyendu Mallick, Debabrata Mukherjee
Summary: In this study, two thermally stable azomethine ylides were isolated, and it was found that they formed N-picoCAAC-CuCl complexes when reacted with CuCl. Computational analysis revealed that the pendant Npy and the softer nature of Cu(I) played crucial roles in this reaction. The resulting complexes can be used as highly active Rh(I) catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Firdaus Rahaman Gayen, Debashree Bora, Dibyendu Mallick, Abir Sarbajna, Subrata Ghosh, Jayaramudu Jarugala, Biswajit Saha
Summary: A ferrocene-functionalized 2-phenylpyridine iridium(III) pentamethylcyclopentadienyl complex was synthesized and investigated for oxygen evolution from water. The high activity of this catalyst can be explained by a proposed Fe(III)/Ir(IV) transient intermediate, where bimetallic redox synergism between the Fe and Ir centers possibly provides an alternative pathway instead of a conventional Ir(V)-based cycle.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Andre Sanchez, Anjali Gurajapu, Wentao Guo, Wang-Yeuk Kong, Croix J. Laconsay, Nicholas S. Settineri, Dean J. Tantillo, Thomas J. Maimone
Summary: Polycyclic ring systems are crucial for the function of biologically active small molecules and organic materials, and slight changes in their molecular shape and connectivity can greatly impact their properties. By utilizing unique molecular topology involving pi-orbital interactions, a common skeletal ancestor can evolve into a complex network of valence isomers, allowing for controllable and continuous isomerization processes with just two chemical steps. Computational and photophysical studies provide insight into the reactivity and mechanism of these isomer networks, which can inform the design and synthesis of new dynamic and shapeshifting systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Priyank Kumar Sharma, Dibyendu Mallick, Soumyajit Das
Summary: A thiophenoradialene-embedded polycyclicheteroterphenoquinone (PHTPQ) derivative with antiaromatic characteristics was synthesized by dehydrogenating its fluorescent dihydro PHTPQ precursor. The compound showed non-emissive and amphoteric redox properties, as well as a visible absorption band extending to 800 nm. Single-crystal analysis revealed a non-aromatic thiophene core and suggested that the pentafulvene subunits exhibited antiaromaticity/paratropicity dominance in the overall ground state properties.
Article
Chemistry, Inorganic & Nuclear
Shriya Saha, Thomas Doughty, Dibyendu Banerjee, Sunil K. Patel, Dibyendu Mallick, E. Siva Subramaniam Iyer, Souvik Roy, Raja Mitra
Summary: A series of organometallic Re(I)(L)(CO)(3)Br complexes with 4'-substituted terpyridine ligands (L) were synthesised and used as electrocatalysts for CO2 reduction. The effect of substitution on the 4'-position of terpyridine on CO2 electroreduction was investigated. All complexes catalyse CO evolution in homogeneous organic media at moderate overpotentials with high faradaic yields. The influence of the pK(a) of the proton sources on the electrochemical catalytic activity was also demonstrated.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Mingchun Gao, Jose M. Ruiz, Emily Jimenez, Anna Lo, Croix J. Laconsay, James C. Fettinger, Dean J. Tantillo, Jared T. Shaw
Summary: Substrates designed for 1,4-C-H insertion to produce benzocyclobutenes underwent a unique elimination reaction, resulting in the formation of ortho-quinone dimethide (o-QDM) intermediates that further participated in Diels-Alder or hetero-Diels-Alder cycloadditions. The analogous benzylic acetals or ethers, on the other hand, bypassed the C-H insertion pathway and, after hydride transfer, underwent a de-aromatizing elimination reaction to form o-QDM at ambient temperature. The resulting dienes exhibited high diastereo- and regio-selectivity when involved in various cycloaddition reactions. This method represents a rare example of catalytic o-QDM generation without the involvement of a benzocyclobutene, and it offers a mild and ambient temperature approach to access these valuable intermediates. DFT calculations provided support for the proposed mechanism. Furthermore, this methodology was successfully applied to the synthesis of (+/-)-isolariciresinol with an overall yield of 41%.
Article
Chemistry, Organic
Hemonta Kumar Saha, Dibyendu Mallick, Soumyajit Das
Summary: In this study, different types of fused compounds were synthesized and their antiaromatic properties were investigated using experimental and computational methods. The results showed that the compound with a sulfone group exhibited the weakest paratropic ring-current strength, while the other compounds showed relatively stronger paratropicity. This can be explained by the electron-withdrawing effect of the sulfone group and the nonaromaticity of the sulfone-containing compound.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hemonta Kumar Saha, Dibyendu Mallick, Soumyajit Das
Summary: Linear and curved isomers of s-indacenodicarbazole were synthesized and characterized to study the tunable paramagnetic behavior of s-indacene. NICS(1)(zz) and ACID calculations were used to analyze the paramagnetic properties. It was found that the curved isomer exhibited stronger antiaromaticity compared to the linear isomer, and this was further supported by experimental results such as red-shifted UV-vis absorption and smaller HOMO-LUMO energy gap.
CHEMICAL COMMUNICATIONS
(2022)