Article
Chemistry, Physical
Mario Prejano, Raffaella Mancuso, Tiziana Marino, Bartolo Gabriele
Summary: In this study, a detailed computational investigation was conducted on the conversion of 1-(methylthio)-3-yn-2-ols to thiophene-3-carboxylate esters using PdI2/KI catalyst. The study provides insights into the role of each species involved in the reaction mechanism and confirms the experimental data.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Yi Zhang, Thirakorn Mokkawes, Sam P. de Visser
Summary: DFT calculations reveal a novel mechanism of aromatic defluorination by P450 Compound I, involving either an epoxide intermediate or a 1,2-fluorine shift in an electrophilic intermediate. The presence of a proton donor is crucial, as a strong Fe-F bond can be formed in the absence of one. This study provides insights into the potential application of cytochrome P450 enzymes in biocatalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yong Wu, Shanshan Cao, Iskander Douair, Laurent Maron, Xihe Bi
Summary: The [2+1] cycloaddition reaction of a metal carbene with an alkene often suffers from side reactions, leading to lower yields of cyclopropanation products. By adding a low concentration of diazo compound to alkenes, it was found that AgOTf catalysis can efficiently produce cyclopropane products from hindered alkenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Hyun Tae Kim, Eunsu Kang, Minkyu Kim, Jung Min Joo
Summary: A new class of bidentate ligands was synthesized through a modular approach involving Rh-catalyzed reactions. These ligands enable Pd-catalyzed C-H alkenylation on electron-rich and sterically less hindered arenes, while facilitating the oxidation of Pd(0) intermediates, potentially finding broad application in transition-metal-catalyzed reactions.
Article
Materials Science, Multidisciplinary
Zeyun Zhang, Xuefei Xu
Summary: In this study, the eNRR performance of 30 single metal atoms supported on a C2N monolayer (M@C2N) was evaluated using density functional theory calculations and the computational hydrogen electrode model. A new thermodynamically stable Pd-W hetero-metal diatomic catalyst supported on the C2N monolayer (PdW@C2N) was also designed. The results showed that PdW@C2N exhibited excellent performance in catalyzing the eNRR process, with low overpotential, ultra-low NH3 desorption free energy, and high selectivity towards eNRR over hydrogen evolution reaction (HER). Compared to its monomer and homonuclear diatom counterparts, PdW@C2N showed superior eNRR performance. The revealed mechanism suggested that the preferential H adsorption over N-2 on the active site may not hinder the eNRR process, especially in heteronuclear diatom catalysts.
ENERGY & ENVIRONMENTAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Rongrong Li, Xinzheng Yang
Summary: Density functional theory computations provide mechanistic insights into Cu and chiral phosphoric acid (CPA) catalyzed enantioconvergent amination of racemic benzenesulfonohydrazide. The O-O bond homolysis of tert-butyl 4-phenylbutaneperoxoate is the turnover-limiting step with a total free energy barrier of 19.1 kcal/mol. Enantioconvergent amination is achieved by obtaining the same intermediate through a prochiral carbon atom. The order and mode of hydrogen atom transfer by CPA and tert-butyloxy significantly influence the enantioselectivity and energy barriers. The olefinic side product generated by beta-hydride elimination is thermodynamically less favorable by 9.9 kcal/mol. A series of phosphoric acids are predicted as promising co-catalysts with lower barriers for O-O bond homolysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Tanmoy Maity, Pameli Ghosh, Soma Das, Debraj Saha, Subratanath Koner
Summary: This study reports the Ullmann C-N coupling reaction of nitroarenes using a copper containing metal-organic framework (MOF) catalyst under heterogenous conditions for the first time. The protocol suppresses by-product formation in catalytic reactions, and the catalyst was designed and synthesized through a two-step post-synthesis functionalization process.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Lang Xu, Eric E. Stangland, James A. Dumesic, Manos Mavrikakis
Summary: Catalytic hydrodechlorination of 1,2-dichloroethane using Pt catalysts was studied through a synergistic approach of DFT calculations, reaction kinetics experiments, and microkinetic modeling. The reaction on Pt(111) involves multiple steps leading to the formation of ethane. Adjustments to model parameters were made to achieve good agreement between theoretical predictions and experimental results, highlighting the importance of coverage effects in catalytic reactions. Overall, the study provides valuable mechanistic insights for improving catalysts in this chemistry.
Article
Chemistry, Inorganic & Nuclear
Jialuo Cai, Cheng Peng, Yong Wang
Summary: This study employed DFT calculations to investigate the mechanism of Ru(II) chelate catalyzed selective functionalization of N-pivaloylindole. The results showed a favorable pathway for C7-H activation and provided mechanistic insights into the observed regioselectivity through distortion-interaction analysis and IRI analysis.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Yingzhe Yu, Jichen Wu, Minhua Zhang
Summary: This study constructed a reaction network of acetylene on Pd-Au catalyst and calculated the adsorption configurations, energies, and electronic properties of important species using DFT. The results showed that acetylene tends to adsorb on sites around Pd atoms and does not occupy the active site of ethylene. DFT calculations also revealed that acetylene is highly reactive and oxidation, hydrogenation, and polymerization reactions are favorable. Among these reactions, oxidation has the most competitive advantage, with CO2 being the major product followed by C2H3. The presence of CO2 and C2H3 does not adversely affect the reaction system, indicating that the trace amount of acetylene in the raw material ethylene has a weak impact on the vinyl acetate reaction system.
APPLIED SURFACE SCIENCE
(2022)
Article
Chemistry, Applied
Min Wen, Shujuan Lu, Chaogang Fan, Kai Shen, Shaohui Lin, Qinmin Pan
Summary: A palladium(II)-coordinated covalent organic framework (Pd(II)@COF) was synthesized mechanochemically and demonstrated as a catalyst for conjugate addition reactions. The catalyst showed good recyclability with >80% yields in the first 4 cycles, broadening the application of COFs in catalysis and providing a new option for Pd(II)-catalysis.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Engineering, Environmental
Peng Zheng, Chengkun Xiao, Shaotong Song, Aijun Duan, Chunming Xu
Summary: The study shows that different Ni-promoted MoS2 edges have varying effects on the hydrodenitrogenation of quinoline, with the morphology of active sites directly affecting the formation of hydrogenation derivatives and denitrogenation products.
JOURNAL OF HAZARDOUS MATERIALS
(2021)
Article
Chemistry, Physical
Rama Moorthy Appa, Jangam Lakshmidevi, Bandameeda Ramesh Naidu, Katta Venkateswarlu
Summary: This paper presents a quick and eco-friendly protocol for the synthesis of symmetrical biaryls using arylboronic acids and Pd(OAc)(2) in water extract of pomegranate ash. The method does not require external base and ligand, resulting in excellent yields under ambient aerobic conditions.
MOLECULAR CATALYSIS
(2021)
Article
Materials Science, Multidisciplinary
Man Jiang, Hui Du, Ao Gan, Muyi Ni, Bin Zhao
Summary: Radiotoxic Po, mainly formed as PbPo, is produced during normal operation of lead-bismuth eutectic in lead-bismuth fast reactors and accelerator-drive systems. Some hazardous PbPo molecules evaporate and accumulate in the cover gas. This study investigated the adsorption and dissociation of PbPo on Pd surfaces using density functional theory. The results showed that PbPo strongly chemisorbs on Pd(100), Pd(110), and Pd(111) surfaces, with adsorption energies ranging from -1.14 eV to -5.36 eV.
JOURNAL OF NUCLEAR MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Zhiwei Lu, Jinpeng Chen, WenLi Wang, Wenjin Li, Mengmeng Sun, Yanying Wang, Xianxiang Wang, Jianshan Ye, Hanbing Rao
Summary: By decorating non-noble electrocatalyst with a layer of biomass derivative nitrogen-doped carbon, the efficiency of the oxygen reduction reaction (ORR) in both alkaline and acid electrolytes can be significantly improved. The resulting catalyst demonstrates comparable catalytic activities to benchmark Pt/C, remarkable survivability to methanol, and preferable long-term stability.
Article
Chemistry, Multidisciplinary
Yongxiang Zheng, Baptiste Moegle, Santanu Ghosh, Anna Perfetto, Davide Luise, Ilaria Ciofini, Laurence Miesch
Summary: A copper-mediated coupling reaction between ynamides and diazo-compounds to produce N-allenamides has been reported, providing a facile and rapid access to terminal N-allenamides with wide functional group compatibility on the nitrogen. This method was successfully applied to the synthesis of fluorine-substituted N-allenamides, which are important building blocks in various fields. DFT calculations provided insights into the mechanism involved in this reaction.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Eric Bremond, Marika Savarese, Nadia Rega, Ilaria Ciofini, Carlo Adamo
Summary: By using different density functional approximations, we reconstructed the free energy profiles along reaction pathways and compared the computed barrier heights of proton transfer reactions using two different methods. The results show that the choice of density functional has a significant impact on the computed results, with local density functionals often underestimating the barrier heights.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Multidisciplinary
Feven Alemu Korsaye, Aurelien de la Lande, Ilaria Ciofini
Summary: This paper presents a density-based method for describing and diagnosing the electronic density evolution in real-time time-dependent density functional theory simulations of a family of organic molecules. By computing charge transfer distance and diagnostic indices, the redistribution of density can be analyzed, and artificial factors in the simulations can be identified.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Davide Luise, Massimo Christian D'Alterio, Giovanni Talarico, Ilaria Ciofini, Frederic Labat
Summary: The absorption spectra of polymers derived from different positions of phenylenediamines were simulated using DFT calculations and TD-DFT simulations. The results were compared with solvated oligomers extracted from periodic structures. The study showed that for ortho- and para-phenylenediamines, modeling solvated dimers already achieved agreement with experimental data, while for meta-phenylenediamine, the inclusion of long-range electrostatic effects is necessary.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2022)
Article
Chemistry, Physical
M. E. Sandoval-Salinas, E. Bremond, A. J. Perez-Jimenez, C. Adamo, J. C. Sancho-Garcia
Summary: A family of non-empirical double-hybrid density functionals based on Perdew-Burke-Ernzerhof (PBE) exchange and correlation functionals is utilized to calculate the excitation energies of linear and cyclic acenes. The calculated energies for different states are compared with experimental results and other double-hybrid expressions. The study demonstrates that these non-empirical functionals outperform hybrid functionals and provide competitive results.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Maciej Spiegel, Carlo Adamo
Summary: Photosensitizers with the Ru(II)-polypyridyl complex structure have shown potential as photodynamic therapy agents for treating neoplasms, but their poor solubility has been a challenge. This study investigates the use of a polyamine macrocycle ring as a solution to improve solubility. The results suggest that protonation of amine groups enhances reactivity, but complexation weakens the desired photoactivity.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Jun Su, Davide Luise, Ilaria Ciofini, Frederic Labat
Summary: We investigate the properties of different bulk MAPbX3 perovskite systems and heterointerface models between MAPI and TiO2, which are key components of perovskite solar cells. Using a combination of periodic and non-periodic calculations, we model the geometric, electronic, and optical properties of these systems and find that they have favorable features for solar devices. Our computational approach proves to be reliable and cost-effective for studying materials related to photovoltaic applications.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Lorenzo Briccolani-Bandini, Eric Bremond, Marco Pagliai, Gianni Cardini, Ilaria Ciofini, Carlo Adamo
Summary: In this study, the double proton transfer (PT) reaction in the complex molecule [2,2'-bipyridyl]-3-3'-diol was explored, revealing the coupling of proton movements with significant rearrangement of the electronic structure. The reaction could occur simultaneously (concerted) or sequentially (stepwise), with the characteristics of the stepwise PT depending on the chosen exchange-correlation functionals. The potential energy surface (PES) and free-energy surface (FES) were analyzed using density functional theory, showing variations in the stepwise mechanism and the presence of stable intermediates and transition states.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Maryam Mansoori Kermani, Hanwei Li, Alistar Ottochian, Orlando Crescenzi, Benjamin G. Janesko, Giovanni Scalmani, Michael J. Frisch, Ilaria Ciofini, Carlo Adamo, Donald G. Truhlar
Summary: Theoretical characterization of reactions of complex molecules requires accurate determination of the relative energies of intermediates and transition states. In this study, the DLPNO-CCSD(T) method was employed to provide benchmark values for Diels-Alder transition states leading to strained pentacyclic adducts. Various wave function and density functional methods were compared for their prediction of absolute and relative barrier heights. The results show that only a few density functionals can satisfactorily predict absolute barrier heights, while relative barrier heights are more accurate. The findings of this study can guide the selection of density functionals for future studies on crowded, strained transition states of large molecules.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Michele Turelli, Ilaria Ciofini, Qinfan Wang, Alistar Ottochian, Frederic Labat, Carlo Adamo
Summary: Organic luminophores with luminescence enhancement in solid state have great potential for the development of functional materials. However, the understanding of the molecular interactions responsible for the macroscopic response is limited. Theoretical frameworks that provide mechanistic explanations and quantitative predictions are important for the understanding of solid-state luminescence enhancement.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Andrew M. Teale, Trygve Helgaker, Andreas Savin, Carlo Adamo, Balint Aradi, Alexei Arbuznikov, Paul W. Ayers, Evert Jan Baerends, Vincenzo Barone, Patrizia Calaminici, Eric Cances, Emily A. Carter, Pratim Kumar Chattaraj, Henry Chermette, Ilaria Ciofini, T. Daniel Crawford, Frank De Proft, John F. Dobson, Claudia Draxl, Thomas Frauenheim, Emmanuel Fromager, Patricio Fuentealba, Laura Gagliardi, Giulia Galli, Jiali Gao, Paul Geerlings, Nikitas Gidopoulos, Peter M. W. Gill, Paola Gori-Giorgi, Andreas Gorling, Tim Gould, Stefan Grimme, Oleg Gritsenko, Hans Jorgen Aagaard Jensen, Erin R. Johnson, Robert O. Jones, Martin Kaupp, Andreas M. Koster, Leeor Kronik, Anna Krylov, Simen Kvaal, Andre Laestadius, Mel Levy, Mathieu Lewin, Shubin Liu, Pierre-Francois Loos, Neepa T. Maitra, Frank Neese, John P. Perdew, Katarzyna Pernal, Pascal Pernot, Piotr Piecuch, Elisa Rebolini, Lucia Reining, Pina Romaniello, Adrienn Ruzsinszky, Dennis R. Salahub, Matthias Scheffler, Peter Schwerdtfeger, Viktor N. Staroverov, Jianwei Sun, Erik Tellgren, David J. Tozer, Samuel B. Trickey, Carsten A. Ullrich, Alberto Vela, Giovanni Vignale, Tomasz A. Wesolowski, Xin Xu, Weitao Yang
Summary: This paper provides an informal review and discussion on the history, present status, and future of density-functional theory (DFT) by 70 workers in the field. The format of a roundtable discussion allowed participants to express their views through 302 individual contributions to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper offers a comprehensive snapshot of DFT in 2022.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Cosimo Micheletti, Qinfan Wang, Francesco Ventura, Michele Turelli, Ilaria Ciofini, Carlo Adamo, Andrea Pucci
Summary: This study explores the preparation of red-emitting luminescent solar concentrators using an aggregation-induced enhanced emission fluorophore and investigates the behavior of the fluorophore in different environments. The results show that by suppressing the aggregation of the fluorophore, the luminescence performance and quantum yield can be improved, leading to enhanced performance of the luminescent solar concentrators.