Rational design of 2D Janus P3m1 M2N3 (M = Cu, Zr, and Hf) and their surface-functionalized derivatives: ferromagnetic, piezoelectric, and photocatalytic properties.

In this study, first-principles calculations were employed to rationally design two-dimensional (2D) Janus transition metal nitrides of P3m1 M2N3 phases, where M is a d-block element (Sc-Zn, Y-Cd, Hf-Hg). Among the 29 examined 2D M2N3, three 2D phases, namely P3m1 Cu2N3, Zr2N3, and Hf2N3, exhibit excellent thermodynamic, dynamic, mechanical, and thermal stabilities. These novel Janus 2D materials exhibit ferromagnetic metallic and half-metallic behavior. The related 2D Janus surface-functionalized derivatives, Cu2N3H, Cu2N3F, Cu2N3Cl, Zr2N3H, Hf2N3H, and Hf2N3F, are all dynamically stable. The 2D Janus P3m1 phases of Zr2N3H, Hf2N3H, and Hf2N3F, all with M in the +IV oxidation state, act as semiconductors in the visible region, with energy band gaps of 2.26-2.70 eV at the HSE06 level of theory. On the other hand, the 2D Janus P3m1 Cu2N3X phases (where X = H, F, and Cl) are ferromagnetic half-metals. Additionally, it has been unveiled that there are high hole mobilities (∼6 × 103 cm2 V-1 s-1) derived from the moderate deformation potential and effective mass in the 2D Janus P3m1 Zr2N3H, Hf2N3H, and Hf2N3F phases. Uniaxial strain engineering has demonstrated the outstanding in-plane piezoelectric properties of 2D Janus P3m1 Zr2N3H, Hf2N3H, and Hf2N3F with high d11 values (∼99.91 pm V-1). Furthermore, the desirable band-edge alignments and high anisotropic carrier mobilities of 2D Janus P3m1 Zr2N3H, Hf2N3H, and Hf2N3F phases indicate their potential as visible light-driven photocatalysts for water splitting reactions on different facets. These properties render 2D Janus P3m1 Zr2N3H, Hf2N3H, and Hf2N3F phases promising for use in optoelectronics, piezoelectric sensing, and photocatalysis applications.

Trans-Concerted Addition to Alkynes: the case of Ynamide Silylzincation.

An original concerted antarafacial mechanism for the addition of diorganosilyl-zinc reagents across the C-C triple bond in ynamides is computationally investigated using DFT calculations. This concerted mechanism, leading to a trans-product in only one step, results in the formation of a Si-C and a Zn-C σ-bonds on opposite sides of the π-system. We demonstrate that the mechanism going through a η2-vinyl intermediate and the proposal of a radical chain pathway are energetically unsustainable. The retained concerted antarafacial pathway is tested on experimental selectivities: the regioselectivity, in favor of the silyl ß-addition in ynamide, and stereoselectivity, which is cis- with (Me2PhSi)2Zn but trans- with [(Me3Si)3Si]2Zn, are well reproduced by DFT calculations. The regio- and stereoselectivity are discussed using the activation strain model and a chemical bonding analysis.

Predicted High-Energy Density MN8 Containing Anionic 18-Crown-6 Ring-Based Polynitrogen Monolayers Acting as Cryptand.

In this study, we investigate the potential of the 18-crown-6-like two-dimensional (2D)-N8 structure to accommodate electrons from metals without compromising its covalent nitrogen network. Employing the crystal structure prediction enhanced by evolutionary algorithm and density functional theory methodology, we successfully predicted the existence of 16 layered M@2D-N8 complexes from a total of 39 MN8 systems investigated at 100 GPa (M = s-block Na-Cs, Be-Ba and d-block Ag, Au, Cd, Hg, Hf, W, and Y). Among those, there are 13 quenchable M@2D-N8 compounds that are dynamically stable at 1 atm. Orbital interactions and bonding analysis show that 2D-N8 presents a flat localized π* band that can accommodate one or two electrons without breaking the 2D covalent nitrogen network. Depending on the metal-to-polynitrogen charge transfer (formally, 1-4 electrons), these N-rich phases are semiconducting or metallic under ambient conditions. Ab initio molecular dynamics simulations show that K(I)@2D-N8 and Ca(II)@2D-N8 are thermally stable up to 600 K, while the Hf(IV)@2D-N8 compound is thermally not viable at 400 K because of the weakening of the N═N bonds due to a strong four-electron reduction. These metal 18-crown-6 ring-based polynitrogen compounds, as expected due to their high nitrogen content (eight nitrogen atoms per metal), could potentially serve as new high-energy density materials.

Expanding horizons in conceptual density functional theory: Novel ensembles and descriptors to decipher reactivity patterns.

Conceptual density functional theory (CDFT) and the quantum reactivity descriptors stemming from it have proven to be valuable tools for understanding the chemical behavior of molecules. This article is presented as being intrinsically of dual character. In a first part, it briefly reviews, in a deliberately didactical way, the main ensembles in CDFT, while the second half presents two additional ensembles, where the chemical hardness acts as a natural variable, and their respective reactivity descriptors. The evaluation of these reactivity descriptors on common organic chemical reagents are presented and discussed.

Accumulation, Characterization and Reactivity of Chiral Ammonium-Carboxonium Dications in Superacid.

The accumulation of chiral ammonium-oxocarbenium dications in superacid is evidenced by low-temperature NMR spectroscopy, X-ray diffraction analysis and confirmed by DFT calculations. Its potential for the diastereoselective remote hydrofunctionalization of non-activated alkene is also explored.

Determination of the Hammett Acidity of HF/Base Reagents.

Harnessing the acidity of HF/base reagents is of paramount importance to improve the efficiency and selectivity of fluorination reactions. Yet, no general method has been reported to evaluate their acidic properties, and experimental designs are still relying on a trial-and-error approach. We report a new method based on 19F NMR spectroscopy which allows highly sensitive measures and short-time analyses. Advantageously, the basic properties of the indicators can be determined upstream by DFT calculations, affording a simple yet robust semiempirical approach. In particular, the indicators used in this study were rationally designed to fit on the conceptually appealing and commonly used Hammett scale. This method has been applied to commercially available and recently developed HF/base reagents.

Acid-Catalyzed Activation and Condensation of the =C5H Bond of Furfural on Aldehydes, an Entry Point to Biobased Monomers.

Furfural is an industrially relevant biobased chemical platform. Unlike classical furan, or C-alkylated furans, which have been previously described in the current literature, the =C5H bond of furfural is unreactive. As a result, on a large scale, C=C and C=O bond hydrogenation/hydrogenolysis is mainly performed, with furfuryl alcohol and methyl tetrahydrofuran being the two main downstream chemicals. Here, we show that the derivatization of the -CHO group of furfural restores the reactivity of its =C5H bond, thus permitting its double condensation on various alkyl aldehydes. Overcoming the recalcitrance of the =C5H bond of furfural has opened an access to a biobased monomer, whose potential have been investigated in the fabrication of renewably-sourced poly(silylether). By means of a combined theoretical-experimental study, a reactivity scale for furfural and its protected derivatives against carbonylated compounds has been established using an electrophilicity descriptor, a means to predict the molecular diversity and complexity this pathway may support, and also to de-risk any project related to this topic. Finally, by using performance criteria for industrial operations in the field of fuels and commodities, we discussed the industrial potential of this work in terms of cost, E-factor, reactor productivity and catalyst consumption.

Exploring Superacid-Promoted Skeletal Reorganization of Aliphatic Nitrogen-Containing Compounds.

Here we report a method to reorganize the core structure of aliphatic unsaturated nitrogen-containing substrates exploiting polyprotonation in superacid solutions. The superelectrophilic activation of N-isopropyl systems allows for the selective formal Csp3 -H activation/cyclization or homologation / functionalization of nitrogen-containing substrates. This study also reveals that this skeletal reorganization can be controlled through protonation interplay. The mechanism of this process involves an original sequence of C-N bond cleavage, isopropyl cation generation and subsequent C-N bond and C-C bond formation. This was demonstrated through in situ NMR analysis and labelling experiments, also confirmed by DFT calculations.

Metallo-dithiaporphyrin pigments for bulk-heterojunction solar cell applications: ab initio investigation of structural and optoelectronic properties.

Metallo-dithiaporphyrin small molecules have been designed by substituting Ru(ii) with various transition metals at the same oxidation state (M = Mn, Fe, Ni, Cu) as donor materials for Bulk Heterojunction Organic Solar Cells (BHJ-OSCs). Density functional theory (DFT) and time-dependent DFT (TD-DFT) have been used to study the optoelectronic properties of metallo-dithiaporphyrin at various functionals and basis sets. We discovered that the open-circuit voltage (VOC) value increases when Ru(ii) in Ru(S2TTP)Cl2 (S2TTP = tetra-p-tolyldithiaporphyrin) is substituted. In addition, the light harvesting efficiency (LHE) of nickel, manganese, and iron complexes was found to be similar to that of ruthenium, and the iron complex furthermore presented a comparable charge transfer in the excited state corresponding to the Q-band, compared to Ru(S2TTP)Cl2. Hence M(S2TTP)Cl2 (M = Mn, Fe, Ni) appear to be potential low cost candidate donor molecules within a bulk heterojunction solar cell. We further propose suitable engineered acceptor pigments, fitted to provide a good overall solar cell efficiency.

Catalytic synthesis of renewable phenol derivatives from biobased furanic derivatives.

Here, we study a sequence Diels-Alder/aromatization reaction between biobased furanic derivatives and alkynes, paving the way to renewable phenols. Guided by DFT calculations, we revealed that, in the case of dimethylfuran, the methyl group can migrate during the aromatization step, making this substrate also eligible to access renewable phenols. This reaction has been then successfully transposed to furfural and furfuryl alcohol, allowing molecular diversity and complexity to be created on phenol ring starting from two cheap biobased furanic derivatives available on large scale.

First-principles structure prediction of two-dimensional HCN polymorphs obtained via formal molecular polymerization.

In the present study, ab initio evolutionary algorithms and heuristic approach were used to predict new two-dimensional (2D) hydrogen cyanide crystalline phases based on HCN and HNC molecular building blocks. Our research revealed thirty-seven 2D HCN and HNC structures within six topological families which contain N1, N2 dimers, N3 trimers, infinite poly-N motifs, or zigzag C-C chains. HSE06 functional calculations indicated that 2D 1Pmn21 HCN, 2Pma2 HCN, 3P21212 HCN, and 6Pbcm HNC are direct semiconductors with band gaps Eg of 5.1, 4.2, 4.3, and 2.8 eV, respectively, and isovalent element substitutions (C by Ge/Si, and H by F) were performed to tune the electronic band gaps of the resulting 2D structures (Eg = 1.2-7.4 eV). Moreover, it has been found that the high in-plane Young's modulus (330.3-445.8 N m-1) and strong tolerance of direct band transitions (Eg = 1.2-5.3 eV) against the external biaxial strains in these four 2D HCN structures endow them with potential applications in photofunctional and flexible electronic devices. Finally, ab initio molecular dynamics simulations showed that at 50 GPa and 400 K, HCN molecules in a bulk I4mm hydrogen cyanide molecular crystal can extend to 2D HCN covalent nets.

Prediction of Two-Dimensional Group IV Nitrides AxNy (A = Sn, Ge, or Si): Diverse Stoichiometric Ratios, Ferromagnetism, and Auxetic Mechanical Property.

In this work, we unveiled a new class of two-dimensional (2D) group IV nitride AxNy (A = Sn, Ge, or Si) prototypes, C2/m A4N, P3̅m1 A3N, P3m1 A2N, P3̅m1 A3N2, P6̅m2 AN, P3̅m1 AN, P6̅2m A3N4, P3m1 A2N3, P4̅21m AN2, and P3̅m1 AN3, by using evolutionary algorithms combined with first-principles calculations. Using HSE06 functional calculations, a wide range of band gaps from metal to semiconductor (0.405-5.050 eV) and ultrahigh carrier mobilities (1-24 × 103 cm2 V-1 s-1) were evidenced in these 2D structures. We found that 2D P3m1 Sn2N3, Ge2N3, and Si2N3 are intrinsic ferromagnetic semiconductors with gaps of 0.677, 1.285, and 2.321 eV, respectively. The lattice symmetry and Si-to-N2 charge transfer upon strain lead to large anisotropic negative Poisson's ratios (-0.281 to -0.146) along whole in-plane directions in 2D P4̅21m SiN2. Our findings not only enrich the family of 2D nitrides but also highlight the promising optoelectronic and nanoauxetic applications of 2D group IV nitrides.

Theoretical exploration of the reactivity of cellulose models under non-thermal plasma conditions-mechanistic and NBO studies.

Mechanistic details of cellulose depolymerization by non-thermal (atmospheric) plasma (NTAP) remains under-explored given the complexity of the medium. In this study, we have investigated the reaction mechanism of glycosidic-bond degradation triggered by reaction with hydroxyl radicals, considered as the principal reactive species in NTAP medium. In the first step of reaction sequence, H-abstraction reactions by HO‧ . radical on different CH sites of the pyranose ring were found to be non-selective and markedly exergonic giving rise to a set of cellobiosyl carboradicals likely to undergo further reactions. We then showed that cellobiosyl carboradicals are protected against direct hydrolysis, no activation of the (1-4)- ß -glycosidic bond being characterized. Interestingly, a simple homolytic bond cleavage allowed to obtain desired monomer. Among the 18 possible fragmentations, involving CC and CO bond breaking from cellobiosyl carboradicals, 14 transition states were successfully identified, and only three reaction pathways proved kinetically and thermodynamically feasible. Natural bond orbital (NBO) analysis was performed to shed light on electronic structures of different compounds.

Hidden Heptacyclic Chiral N-Acyl Iminium Ions: A New Entry to Enantioenriched Polycyclic Azepanes and Azocanes by Superacid-Promoted Intramolecular Pictet-Spengler Reaction.

Enantioenriched complex fused-tricyclic azepanes or bridged-polycyclic azocanes were constructed via a two-step sequence involving an enantioselective organocascade followed by superacid activation of the domino adduct. The activated oxa-bridged azepane acts as a key hidden heptacyclic chiral N-acyl iminium ion triggering a chemo- and diastereoselective intramolecular mono- or di-arylation.

Polarisation of Electron Density and Electronic Effects: Revisiting the Carbon-Halogen Bonds.

Electronic effects (inductive and mesomeric) are of fundamental importance to understand the reactivity and selectivity of a molecule. In this article, polarisation temperature is used as a principal index to describe how electronic effects propagate in halogeno-alkanes and halogeno-alkenes. It is found that as chain length increases, polarisation temperature decreases. As expected, polarisation is much larger for alkenes than for alkanes. Finally, the polarisation mode of the carbon-fluorine bond is found to be quite different and might explain the unusual reactivity of fluoride compounds.

Phase diagram exploration of Tc-Al-B: from bulk Tc2AlB2 to two-dimensional Tc2B2.

In this study, the ternary phase diagram of the Tc-Al-B system is constructed by a combination of an evolutionary algorithm and density functional theory calculations. Four novel phases are predicted, including three binary compounds (P1̄ Al7B15, Cmcm TcAl2, and C2 TcAl3) and one ternary compound (Cmmm Tc2AlB2). All predicted structures are mechanically, dynamically, and thermodynamically stable. Among the predicted phases, P1̄ Al7B15 resembles the experimental structure of Al0.93B2 and Cmmm Tc2AlB2 corresponds to the 212-type MAB phase. Due to the in- and out-of-plane anisotropic chemical bonding in Cmmm Tc2AlB2, a tetragonal two-dimensional (2D) Tc2B2 structure could be possibly exfoliated by chemical removal of Al atoms. The electronic structure calculations indicate that the 2D Tc2B2 structure and its potential layered precursors are all metallic. Furthermore, the chemical reactivity of H, F, O and, OH ligands with the 2D Tc2B2 surface is studied and the associated 2D surface-functionalized Tc2B2 derivatives are found to be metallic. It is revealed that the F and O functional groups strengthen the surface atomic layer of 2D Tc2B2 and enhance the Young's moduli.

Understanding the intermolecular Diels-Alder cycloaddition promotion: Activation strain model/energy decomposition analysis model and conceptual density functional theory viewpoints.

The present work reports the computational study of the major Diels-Alder reaction between 2-bromocycloalkenone and a variety of mono- and di-substituted dienes. Through density functional theory (DFT) calculations and subsequent activation strain model/energy decomposition analysis/conceptual DFT (C-DFT) analyses, the key factors governing the activation barriers heights, and thus reactivity, are characterized. In contrast with a previous study, steric effects do not appear to control reactivity. Conversely, in all presented cases, a subtle interplay between deformation and interaction energies is evidenced at transition states. In the end, neither term alone is enough to explain or predict reactivity. Yet a simple C-DFT descriptor allows to predict with a reasonable efficiency the activation barriers: the excitation energy needed to observe a charge transfer from the diene to the dienophile. Theoretical elements are provided to support the use of this descriptor.

Prediction of allotropes of tellurium with molecular, one- and two-dimensional covalent nets for photofunctional applications.

In the present work, three new semiconducting two-dimensional (2D) Te phases containing three- and four-coordinated Te centers were proposed by using evolutionary algorithms combined with first-principles calculations. Using density functional theory calculations, we discussed the bonding and electronic properties in these phases, and subsequently rationalized their structures. The viability of these predicted structures was demonstrated by evaluating their thermodynamic, dynamic, mechanical, and thermal stabilities. Moreover, a significant direct band gap (0.951-1.512 eV) and excellent transport properties were evidenced in 2D Te nets, which suggests that they could be promising photovoltaic materials candidates. This is further supported by the stability of the associated bulk layered counterparts of the 2D Te nets.

A Combined Experimental-Theoretical Study on Diels-Alder Reaction with Bio-Based Furfural: Towards Renewable Aromatics.

The synthesis of relevant renewable aromatics from bio-based furfural derivatives and cheap alkenes is carried out by using a Diels-Alder/aromatization sequence. The prediction and the control of the ortho/meta selectivity in the Diels-Alder step is an important issue to pave the way to a wide range of renewable aromatics, but it remains a challenging task. A combined experimental-theoretical approach reveals that, as a general trend, ortho and meta cycloadducts are the kinetic and thermodynamic products, respectively. The nature of substituents, both on the dienes and dienophiles, significantly impacts the feasibility of the reaction, through a modulation on the nucleo- and electrophilicity of the reagents, as well as the ortho/meta ratio. We show that the ortho/meta selectivity at the reaction equilibrium stems from a subtle interplay between charge interactions, favoring the ortho products, and steric interactions, favoring the meta isomers. This work also points towards a path to optimize the aromatization step.

A statistical thermodynamics view of electron density polarisation: application to chemical selectivity.

A fundamental link between conceptual density functional theory and statistical thermodynamics is herein drawn, showing that intermolecular electrostatic interactions can be understood in terms of effective work and heat exchange. From a more detailed analysis of the heat exchange in a perturbation theory framework, an associated entropy can be subsequently derived, which appears to be a suitable descriptor for the local polarisability of the electron density. A general rule of thumb is evidenced: the more the perturbation can be spread, both through space and among the excited states, the larger the heat exchange and entropy.