Editorial Material
Chemistry, Multidisciplinary
Dipankar Sahoo, Diana A. Iovan
Summary: A recent study reported the isolation and characterization of an N-trifluoromethyl-substituted Fe(IV) bisimido species that undergoes intramolecular C-H activation. This discovery opens up new possibilities for N-group-transfer chemistry.
Article
Chemistry, Multidisciplinary
Jaime Ponce-de-Leon, Guillermo Marcos-Ayuso, Juan A. Casares, Pablo Espinet
Summary: An efficient Pd/Cu bimetallic cross-coupling catalysis for fluoroaryl halides and fluoroarenes is reported. The in situ generation of Cu nucleophile through rate-determining C-H activation of highly fluorinated aryls (>=4 F atoms) leads to high selectivity in cross-coupling reactions with minimal formation of homocoupling products.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Felix Otte, Johannes Kleinheider, Wolf Hiller, Ruimin Wang, Ulli Englert, Carsten Strohmann
Summary: The halogen bonded adduct between quinuclidine and iodobenzene exhibits the longest N·I molecular halogen bond with a distance of 2.9301(4) angstrom. Topological analysis identified XB as a directional but weak 6-hole interaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Xiaoming Wang, Xin Xu
Summary: Eco-friendly zinc dihydrides stabilized by N-heterocyclic carbenes were shown to be highly efficient catalysts for the double hydroboration of nitriles with pinacolborane, yielding diboronated amines with excellent yields and good functional group tolerance. A single Zn-H insertion product isolated from a stoichiometric reaction of zinc dihydride with nitrile was identified as an active species in this transformation. Kinetic studies provided insights into the catalytic reactions, and zinc dihydride species also exhibited high activity for the hydroboration of imines to boronated amines.
Article
Engineering, Environmental
Dejian Chen, Kunyuan Xu, Mingwei Yang, Jie Hu, Renfu Li, Decai Huang, Sisi Liang, Kun He, Linfeng Yuan, Shujian Wang, Cong Zhou, Jiaxuan Zhang, Haomiao Zhu
Summary: A surface chemistry engineering strategy is proposed for synthesizing robust CsPbX3 (X = Cl, Br, I) nanocrystals in non-toxic ethanol-based solvent. The obtained unsealed CsPbX3 nanocrystals show unprecedented year-long stability in ethanol. Furthermore, water post-treatment can significantly decrease surface defects of the nanocrystals, leading to improved emission efficiency and high photocatalytic efficiency.
CHEMICAL ENGINEERING JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Changseok Lee, Hyung-Joon Kang, Sungwoo Hong
Summary: The formation of C-N bonds through hydroamination reactions catalyzed by nickel hydrides has been a topic of recent interest. This approach offers a way to efficiently transform a variety of alkene and alkyne substrates into compounds enriched with C-N bonds. The review provides a concise overview of the underlying reaction mechanisms and aims to stimulate further progress in NiH-catalytic techniques and catalyst design.
Article
Chemistry, Inorganic & Nuclear
Sara Fernandez-Moyano, Marconi N. Penas-Defrutos, Camino Bartolome, Pablo Espinet
Summary: Analysis of bonding contributions in transition metal complexes [(MCp)-Cp-III*(L)XY] (M = Rh, Ir; Cp* = C5Me5; L = CO, CN-, CNR) revealed a variety of new interactions, including direct lateral donations and hybrid donations, accounting for approximately 20% of the electron donation to the pi*(CO) orbitals.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Magdalena Tarnacka, Ewa Kaminska, Marian Paluch, Kamil Kaminski
Summary: In this study, the annealing of confined S-methoxy-PC within alumina and silica porous membranes was investigated using dielectric spectroscopy. It was found that the structural dynamics of confined S-methoxy-PC significantly slowed down below and above the glass transition temperature of the interfacial layer. Unexpectedly, a change in the temperature dependence of the characteristic time scale was observed at the glass transition temperature for all confined samples. Modeling results suggested that the decrease in pore radius caused by the vitrification of interfacial molecules contributed to the observed variation in the characteristic time scale.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Nolwenn Mahieu, Jakub Piatkowski, Thomas Simler, Gregory Nocton
Summary: At the beginning of the development of structural organometallic chemistry, the interest in LnCp(3) complexes quickly diminished due to the electrostatic nature of bonding between pi-aromatic ligands and 4f-elements. However, over the past 70 years, this field has evolved in various directions, showing multiple catalytic reactivities, potential in small molecule activation, and rich redox chemistry. Understanding their electronic nature has been crucial for developing compounds with tailored magnetic and fluorescence properties that have gained popularity in recent years. Future developments will benefit from detailed studies in reactivity, structure, and physical chemistry, particularly in photochemistry, electro- or photoelectrocatalysis, and quantum technology spin manipulation.
Article
Chemistry, Multidisciplinary
Maximilian Dietz, Merle Arrowsmith, Lukas Endres, Valerie Paprocki, Bernd Engels, Holger Braunschweig
Summary: A study found that stable pogo-stick complexes can be synthesized through a series of reactions, and their characteristics were confirmed by infrared spectroscopy and X-ray crystallography. These complexes exhibited strong absorption in the near-infrared region. Theoretical calculations further elucidated the mechanism of these absorptions. Additionally, the complexes can react with other compounds to form new substances.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Medicinal
Marta Queizan, Marta Sanchez-Lozano, Marcos Mandado, Jose M. Hermida-Ramon
Summary: By combining multiple hydrogen bonds and anion-pi interactions, neutral metal-free receptors are capable of recognizing anions in highly polar solvents. An aromatic molecular tweezer functionalized with azo groups efficiently captures anions in water, exhibiting high thermodynamic stability and strong bonding within the system. Theoretical and first-principles quantum methods confirm the stability of the anion-tweezer complex over time, with the anion consistently located within the cavity of the tweezer.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2021)
Article
Chemistry, Multidisciplinary
Miaomiao Zhu, Zhengqi Chai, Ze-Jie Lv, Tianyu Li, Wei Liu, Junnian Wei, Wen-Xiong Zhang
Summary: In this study, we demonstrate the controllable cleavage of active and inert C-C bonds within biphenylene through the reaction with potassium graphite and rare-earth complexes with different metal centers. The Caryl-Caryl single bond is activated, producing 9-scandafluorene, when scandium is used as the reaction center. On the other hand, the aromatic ring in biphenylene undergoes ring contraction to form benzopentalene dianionic lutetium when Lu is the reaction center. The selectivity and reaction mechanism are elucidated by isolating intermediates and conducting DFT calculations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Ivan A. Berezianko, Irina V. Vasilenko, Sergei V. Kostjuk
Summary: Silica gel supported ionic liquid catalysts (SILCs) showed excellent activity and selectivity in the polymerization reaction. The addition of fresh catalysts after each polymerization run allowed for the retention of high catalytic activity, enabling multiple successful polymerization cycles.
Article
Chemistry, Inorganic & Nuclear
Li-Hui Hong, Wei-Jung Feng, Wei-Chih Chen, Yu-Chang Chang
Summary: We synthesized a palladium complex (1a) with two different P-donors and proved its effectiveness as a Pd(ii) precatalyst for carbon-phosphorus bond formation. The complex exhibited efficient catalytic activity for the Hirao coupling reaction under environmentally benign conditions. Mechanistic studies were conducted to investigate the generation of plausible Pd(0) active species. The use of bulky di(1-adamantyl)phosphine oxide as a preligand and less bulky di-p-tolylphosphine oxide as the substrate in the coupling reaction was also demonstrated.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Gaoji Wang, Harlei Martin, Susana Amezqueta, Clara Rafols, Goran Angelovski, Celia S. Bonnet
Summary: Zn ions are important in diseases and monitoring their distribution in tissues is clinically significant. This study presents a Zn-sensitive probe based on Gd-DO3A modified with tyrosine and di(2-picolyl)amine chelator, enabling remarkable MRI response. Investigations on the probe's properties upon interaction with Zn2+ reveal selective interaction and substantial changes in the coordination sphere, along with aggregation that enhances relaxivity response. Furthermore, the probe interacts weakly with human serum albumin in the presence of Zn2+, demonstrating the importance of Zn2+ coordination sphere.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Eva Zunzunegui-Bru, Elisabeth Gruber, Stefan Bergmeister, Miriam Meyer, Fabio Zappa, Massimiliano Bartolomei, Fernando Pirani, Pablo Villarreal, Tomas Gonzalez-Lezana, Paul Scheier
Summary: In this study, helium clusters around SF6+ and SF5+ ions were investigated using a combination of experimental and theoretical approaches. The analysis of ion yields and molecular dynamics calculations revealed the existence of stable configurations at specific sizes for the helium clusters interacting with the ions. This research provides new insights into the energetics and structure of He-N-SF6+ and He-N-SF5+ clusters.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Multidisciplinary Sciences
Federico Palazzetti, Cecilia Coletti, Alessandro Marrone, Fernando Pirani
Summary: Multidimensional potential energy surfaces for heavy noble gas-propylene oxide systems were obtained using a phenomenological method. These surfaces, solely determined by anisotropic van der Waals interaction components, were given in an analytical form and can easily be used in molecular simulations. The study identified several potential energy minima on the surfaces, which were verified and characterized using high level ab initio calculations.
Article
Chemistry, Inorganic & Nuclear
Diego Sorbelli, Elisa Rossi, Remco W. A. Havenith, Johannes E. M. N. Klein, Leonardo Belpassi, Paola Belanzoni
Summary: The study investigates the properties and influencing factors of the reactions between gold-aluminyl and gold-boryl complexes with CO2. The results show that the gold-aluminyl and gold-boryl bonds have similar electron-sharing properties, with the gold-boryl bond being slightly more polarized, resulting in lower radical reactivity. Under the influence of ligands, aluminyl products are favored over boryl products, and the gold ancillary ligand has minimal impact on the formation and stability of the reaction products, while carbene ligands are slightly better than phosphine ligands. Furthermore, the steric hindrance at the carbene ligand site plays an important role in the formation of the reaction product.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Matteo De Santis, Diego Sorbelli, Valerie Vallet, Andre Severo Pereira Gomes, Loriano Storchi, Leonardo Belpassi
Summary: This paper extends the four-component relativistic Dirac-Kohn-Sham method to include environmental and confinement effects in the frozen density embedding (FDE) scheme. The implementation is facilitated by the BERTHA code's python API (PyBERTHA) and auxiliary density fitting techniques. The accuracy and numerical stability of the implementation are demonstrated on the NH3-H2O system and the computational performance is evaluated on gold clusters and heavy elements. The results show that FDE improves upon current approximations and provides a basis for generating more realistic radial potentials for confined atoms.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Multidisciplinary
Diego Sorbelli, Leonardo Belpassi, Paola Belanzoni
Summary: The study reports the unprecedented reactivity of coinage metal-aluminyl complexes with dihydrogen. Similar to group 14 dimetallenes and dimetallynes, these complexes are predicted to activate H-2 under mild conditions. Two different reaction pathways are found, revealing a common driving force - the nucleophilic behavior of the electron-sharing M-Al (M = Cu, Ag, Au) bond, enabling a cooperative and diradical-like mechanism. This mode of chemical reactivity emerges as a new paradigm for dihydrogen activation and calls for experimental feedback.
Article
Chemistry, Multidisciplinary
Stefano Falcinelli, Franco Vecchiocattivi, Fernando Pirani
Summary: The authors propose an optical potential formulation to describe the topology of prototypical chemi-ionization reactions of excited state neon with argon, nitrogen, and ammonia molecules. The stereo-dynamic topology of chemi-ionizations is related to the centrifugal barrier of colliding reactants, which acts as a selector of the orbital quantum number effective for reaction in a state-to-state treatment. The accurate formulation of the Optical interaction potentials obtained by the combined analysis of scattering and spectroscopic experimental findings sheds light on the structure, energy, and angular momentum couplings of the precursor state controlling the stereo-dynamics of prototypical chemi-ionization reactions.
COMMUNICATIONS CHEMISTRY
(2023)
Article
Chemistry, Physical
Esther Garcia-Arroyo, Jose Campos-Martinez, Massimiliano Bartolomei, Marta I. Hernandez, Fernando Pirani, Nadine Halberstadt
Summary: In this study, an adiabatic separation of the rotational motion of H2 molecules is applied to build effective pseudoatom-ion potentials for (H2)nNa+/Cl- clusters. The accuracy of this adiabatic model is confirmed by comparing with simulations that explicitly describe molecular rotations. Additionally, differences in cluster stabilities and coordination shells are found depending on the spin isomer, particularly for anionic clusters.
Article
Optics
Qizhen Hong, Loriano Storchi, Massimiliano Bartolomei, Fernando Pirani, Quanhua Sun, Cecilia Coletti
Summary: Rate coefficients for vibrational energy transfer between molecular nitrogen and hydrogen were calculated using a mixed quantum-classical method. These data are crucial for simulating discharges in N-2/H-2 plasma and atmospheric/interstellar medium chemistry. The obtained rates differed significantly from those predicted by first-order perturbation theories. Additionally, different Machine Learning models based on Gaussian Process or Neural Network techniques were analyzed to generate complete datasets of inelastic scattering rate coefficients.
EUROPEAN PHYSICAL JOURNAL D
(2023)
Article
Chemistry, Physical
Diego Sorbelli, Paola Belanzoni, Loriano Storchi, Olivia Bizzarri, Beatrice Bizzarri, Edoardo Mosconi, Leonardo Belpassi
Summary: The Energy Decomposition Analysis in combination with Natural Orbitals for Chemical Valence (EDANOCV) is a powerful tool for analyzing chemical bonds. However, the current implementation neglects spin-orbit coupling effects, limiting its applicability. In this study, we extend the method to include relativistic effects and demonstrate its correctness and stability in simple molecular systems. We also apply the method to analyze the metal-ethylene coordination bond in the group 6-element series to understand its behavior involving heavy and superheavy atoms.
Article
Biochemistry & Molecular Biology
Luca Schio, Michele Alagia, Robert Richter, Vitali Zhaunerchyk, Stefano Stranges, Fernando Pirani, Franco Vecchiocattivi, Marco Parriani, Stefano Falcinelli
Summary: The behavior of nitrosyl chloride (ClNO) exposed to ionizing radiation was studied by directly probing valence-shell electrons in temporal coincidence with ions originating from the fragmentation process of transient ClNO2+. A molecular dication, ClNO2+, was produced through double photoionization with synchrotron radiation. The experiment was conducted at the Elettra Synchrotron Facility of Basovizza (Trieste, Italy) with a linearly polarized light beam parallel to the ClNO molecular beam axis. The double ionization threshold energy of ClNO and six dissociation channels producing various ion pairs have been measured.
Article
Chemistry, Inorganic & Nuclear
Jacopo Segato, Eleonora Aneggi, Walter Baratta, Filippo Campagnolo, Leonardo Belpassi, Paola Belanzoni, Daniele Zuccaccia
Summary: The ion pairing structure of gold(III) catalysts during the hydration of alkynes has been determined through experimental and theoretical analysis. The choice of ligands can control the position of the counterion, affecting the reaction.
Review
Chemistry, Physical
Stefano Falcinelli, David Cappelletti, Franco Vecchiocattivi, Fernando Pirani
Summary: The present review focuses on the role of the precursor state in controlling the dynamical evolution of elementary processes. The structures and stability of the precursor state are difficult to characterize quantitatively. The formulation of intermolecular forces and the application of phenomenological methods have provided important insights into understanding the precursor state and its evolution. This information is particularly valuable for chemi-ionization reactions and has the potential to benefit other elementary processes.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Qizhen Hong, Loriano Storchi, Quanhua Sun, Massimiliano Bartolomei, Fernando Pirani, Cecilia Coletti
Summary: In this study, complete data sets of vibration-to-vibration and vibration-to-translation rate coefficients for N-2-N-2 collisions, as well as transport properties, were calculated in the temperature range 100-9000 K. The improved mixed quantum-classical dynamics approach allowed for more realistic and flexible representations, and the role of intra- and intermolecular potentials on the rates and properties was analyzed. The obtained values are reliable and valuable for communities studying nonlocal thermal equilibrium conditions.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Biochemistry & Molecular Biology
Maria Rutigliano, Fernando Pirani
Summary: The adsorption of nitrogen molecules on a (100) tungsten surface has been studied using a new potential energy surface. Molecular dynamics simulations with a semiclassical collisional method were performed, which included the interaction with surface phonons. The results showed good agreement with experimental data and improved upon previous calculations using Density Functional Theory and long-range van der Waals corrections. Additionally, the dependence of trapping probability on surface temperature for a given collision energy was investigated.
Article
Chemistry, Physical
A. Kurnosov, M. Cacciatore, F. Pirani
Summary: In this study, vibration-to-vibration (VV') exchanges between excited CO and unexcited O2 were investigated using the semiclassical coupled state method. The VV' rate constants were calculated based on a recently proposed accurate surface for the N2-O2 system. The results showed good agreement with experimental determinations.
CHEMICAL PHYSICS LETTERS
(2023)