Search

Metal halide perovskites (MHPs) are characterized as strongly anharmonic and dynamic lattices. While there is a consensus on the solvation-like polarization effect in these materials, whether static polarization, that is, ferroelectricity, exists or not in 3D MHPs remains controversial. In this Review, we resolve this controversy by analysing the stereochemical expression (SE) of the ns2 electron pair (NSEP) on group IV metal cations. The SE-NSEP is key to lattice instability, which governs the breaking of inversion symmetry and induces ferroelectricity. The SE-NSEP is diminishingly small in commonly studied 3D lead iodide or bromide perovskites, indicating an absence of ferroelectricity. In contrast, 2D MHPs promote the SE-NSEP and produce unambiguous ferroelectricity or antiferroelectricity. Irrespective of ferroelectricity, the dynamic manifestation of the SE-NSEP provides the missing link to understanding polar fluctuations and efficient dielectric screening in MHPs, thus, contributing to the long carrier lifetimes and diffusion lengths. This Review establishes a unifying structure–property relationship among chemical composition, centrosymmetry breaking, lattice anharmonicity, ferroelectricity, dielectric screening and the Rashba effect in metal halide perovskites from the perspective of stereochemical expression of ns2 electron pairs on group IV metal cations.

Over the last two decades, the local approximation has been successfully used to extend the range of applicability of the "gold standard" singles and doubles coupled-cluster method with perturbative triples CCSD(T) to systems with hundreds of atoms. The local approximation error grows in absolute value with the increasing system size, i.e., by increasing the number of electron pairs in the system. In this study, we demonstrate that the recently introduced two-point extrapolation scheme for approaching the complete pair natural orbital (PNOs) space limit in domain-based pair natural orbital CCSD(T) calculations drastically reduces the dependence of the error on the system size, thus opening up unprecedented opportunities for the calculation of benchmark quality relative energies for large systems.

Antimony-based metal halide hybrids have attracted enormous attention due to the stereoactive 5s2 electron pair that drives intense triplet broadband emission. However, energy/charge transfer has been rarely achieved for Sb3+-doped materials. Herein, Sb3+ ions are homogeneously doped into 2D [NH3(CH2)4NH3]CdBr4 perovskite (Cd-PVK) using a wet-chemical method. Compared to the weak singlet exciton emission of Cd-PVK at 380 nm, 0.01% Sb3+-doped Cd-PVK exhibits intense triplet emission located at 640 nm with a near-unity quantum yield. Further increasing the doping concentration of Sb3+ completely quenches singlet exciton emission of Cd-PVK, concurrently with enhanced Sb3+ triplet emission. Delayed luminescence and femtosecond-transient absorption studies suggest that Sb3+ emission originates from exciton transfer (ET) from Cd-PVK host to Sb3+ dopant, while such ET cannot occur with Pb2+-doped Cd-PVK because of the mismatch of energy levels. In addition, density function theory calculations indicate that the introduced Sb3+ likely replace the Cd2+ ions along with the deprotonation of butanediammonium for charge balance, instead of generating Cd2+ vacancies. This work provides a deeper understanding of the ET of Sb3+-doped Cd-PVK and suggests an effective strategy to achieve efficient triplet Sb3+ emission beyond 0D Cl-based hybrids.

The η2-formyl borane system 3 is readily available by carbonylation of the vicinal P/BH frustrated Lewis pair (FLP) 1. It serves as a frustrated C/B Lewis pair toward carbon dioxide or phenylisocyanate. In the presence of B(C6F5)3, it forms the coupling product between two CO-derived units. The resulting compound 13 rearranged to a doubly O-borylated endiolate, with both of the central carbon atoms originating from carbon monoxide. The subsequent treatment with a silane gave a rare macrocyclic silicon endiolate.

It has long been known that there is a fundamental difference in the electronic structures of CH5- and SiH5-, two isoelectronic molecules. The former is a saddle point for the SN2 exchange reaction H- + CH4 → [CH5-]‡ → CH4 + H-, while the latter is a stable molecule that is bound relative to SiH4 + H-. SCGVB calculations indicate that this difference is the result of a dramatic difference in the nature of the axial electron pairs in these anions. In SiH5-, the axial pairs represent two stable bonds-a weak recoupled pair bond dyad. In CH5-, the axial electron pairs represent an intermediate transition between the electron pairs in the reactants and those in the products. Furthermore, the axial orbitals at the saddle point in CH5- are highly overlapping, giving rise to strong Pauli repulsion and a high barrier for the SN2 exchange reaction.

The reaction of the intramolecular germylene‐phosphine Lewis pair (o‐PPh2)C6H4GeAr* (1) with Group 15 element trichlorides ECl3 (E=P, As, Sb) was investigated. After oxidative addition, the resulting compounds (o‐PPh2)C6H4(Ar*)Ge(Cl)ECl2 (2: E=P, 3: E=As, 4: E=Sb) were reduced by using sodium metal or LiHBEt3. The molecular structures of the phosphine‐stabilized phosphinidene (o‐PPh2)C6H4(Ar*)Ge(Cl)P (5), arsinidene (o‐PPh2)C6H4(Ar*)Ge(Cl)As (6) and stibinidene (o‐PPh2)C6H4(Ar*)Ge(Cl)Sb (7) are presented; they feature a two‐coordinate low‐valent Group 15 element. After chloride abstraction, a cyclic germaphosphene [(o‐PPh2)C6H4(Ar*)GeP] [B(C6H3(CF3)2)4] (8) was isolated. The 31P NMR data of the germaphosphene were compared with literature examples and analyzed by quantum chemical calculations. The phosphinidene was treated with [iBu2AlH]2, and the product of an Al−H addition to the low‐valent phosphorus atom (o‐PPh2)C6H4(Ar*)Ge(H)P(H)Al(C4H9)2 (9) was characterized., Treating a germylene‐phosphine Lewis pair, 1, with trichlorides of phosphorus, arsenic, and antimony allowed the isolation of oxidative addition products. Reduction of these compounds with sodium metal or LiBHEt3 led to the synthesis of a phosphinidene, an arsinidene and a stibinidene. After halide abstraction, a germaphosphene, 8, was isolated, and its 31P NMR data were analyzed by using quantum chemical calculations. The product of an Al−H addition was found upon treating the phosphinidene with [iBu2AlH]2.

A semi-phenomenological model of a many-particle system of 4He atoms is proposed, in which a helium atom is considered as a complex consisting of a nucleus and a bound pair of electrons in the singlet state. At zero temperature, there are two Bose-Einstein condensates of particles with opposite charges, namely, a condensate of positively charged nuclei and a condensate of negatively charged electron pairs. It is shown that in such a system there exist two excitation branches: sound and optical. On the basis of this model an interpretation of experiments on the study of the eltctrical activity of superfluid heliun is proposed. The frequency at which the resonant absorption of a microwave radiation is observed is interpreted as a gap in the optical branch. It is shown that the distribution of the electric potential in a standing wave in a resonator is similar to that observed experimentally., Comment: 8 pages, 2 figures

In the few past years, the chemistry of frustrated Lewis pairs (FLP) has enabled a plethora of transformations that would otherwise only be possible using transition metal catalysts. Of particular interest are C–H bond activation and borylation reactions, which are the subject of this review. The FLP borylation chemistry is compared with the early borylation methodologies using strongly electrophilic borenium ions. We present the mechanism of the C–H borylation using inter- and intramolecular Lewis pairs, along with some applications of these transformations.1 Introduction2 Electrophilic Borylation3 Intramolecular or Directed Electrophilic Borylation4 Intermolecular FLP-Mediated C–H Borylation5 Stoichiometric Borylation by Intramolecular FLPs5.1 Csp–H Borylation5.2 Csp2–H Borylation5.3 Csp3–H Borylation6 Catalytic Borylation by Intramolecular FLPs7 Catalytic Borylation by Self-Assembled FLPs8 Conclusion

[EN] High-pressure synchrotron X-ray diffraction studies of cobalt iodate, Co(IO3)(2), reveal a counterintuitive pressure-induced expansion along certain crystallographic directions. High-pressure Raman and infrared spectroscopy, combined with density-functional theory calculations, reveal that with increasing pressure, it becomes energetically favorable for certain I-O bonds to increase in length over the full range of pressure studied up to 28 GPa. This phenomenon is driven by the high-pressure behavior of iodate ion lone electron pairs. Two pressure-induced isosymmetric monoclinic-monoclinic phase transitions are observed at around 3.0 and 9.0 GPa, which are characterized by increasing oxygen coordination of the iodine atoms and the probable formation of pressure-induced metavalent bonds. Pressure-volume equations of state are presented, as well as a detailed discussion of the pressure dependences of the observed Raman- and infrared-active modes, which clarifies previous inconsistencies in the literature., This work was supported by the Generalitat Valenciana under Project PROMETEO 2018/123-EFIMAT and by the Spanish Ministerio de Ciencia, Universidades, e Investigacion under Projects PID2019-106383GB-41/42/43, as well as through MALTA Consolider Team research network (RED2018102612-T). A.M. and P.R.-H. acknowledge computing time provided by Red Espan~ola de Supercomputacion (RES) and the MALTA Consolider Team cluster. D.E. acknowledges the resources and technical assistance provided by the Informatics Service of Universitat de Valencia through the Tirant III cluster. A.L. and D.E. would like to thank the Generalitat Valenciana for the Ph.D. Fellowship no. GRISOLIAP/2019/025. R.T. acknowledges funding from the Spanish Ministerio de Economia y Competitividad (MINECO) via the Juan de la Cierva Formacion fellowship (FJC2018-036185-I). C.P. is thankful for the financial support of the Spanish Mineco Project no. FIS2017-83295-P. E.B would like to thank the University of Valencia for his "Attraccio de Talent" postdoctoral contract (UV-INV_POSTDOC19-1026935). The authors thank Sandrine Beauquis from Symme, Universite Savoie Mont Blanc (France), for her technical assistance concerning the SEM and ADX analyses. PXRD experiments were performed at the MSPD beamline of ALBA Synchrotron (experiment no. 2019083663). IR experiments were performed at the MIRAS beamline of ALBA Synchrotron (experiment no. 2020024118).

Attachment of a pair of P-stereogenic mesityl(alkynyl)phosphanyl groups at the 4- and 5-positions of a 9,9-dimethylxanthene framework gave mixtures of the respective rac- and meso-bisphosphanyl diastereoisomers. They slowly epimerized in a thermally induced reaction with Gibbs activation barriers of about 25 kcal mol-1 at room temperature (measured and DFT calculated). The reaction of the meso-mesityl(tert-butylethynyl)phosphanyl derivative with two molar equivalents of Piers' borane [HB(C6 F5 )2 ] led to the formation of the alkylidene-bridged geminal bisphosphane/borane-frustrated Lewis pair system. The compound was obtained enriched (>85 %) in the rac diastereoisomer. With a variety of bifunctional donor substrates, the rac-bis-P/B FLP formed macrocyclic compounds. They were all formally derived from meso-configurated diastereoisomers of the bisphosphanylxanthene backbone.

A novel stable donor/acceptor-supported MnI -metallasilanone 3 was synthesized. The intramolecular silanone-MnI interaction induces a highly strained three-membered cyclic structure, leading to an exceptionally high reactivity of 3 as a donor/acceptor complex of silanone. Indeed, metallasilanone 3 readily reacts with various small molecules such as H2 or ethylene gas in mild conditions.

The cyclopropane ring-opening reaction of riolozatrione, a natural product obtained from Jatropha dioica, afforded a 2,2-disubstituted 1,3-cyclohexandione displaying an alkyl methyl ether group at position 5. The conformational analysis of this product showed a high preference for the trans-diaxial conformation in both solution and solid state. Such conformation was possible from the noncovalent intramolecular nX → π*C═O interactions (X = an element having an unshared electron pair), allowing the determination of the interaction energies. Since the nX → π*C═O interactions can be regarded as additive, the energy values ranged from 4.52 to 6.51 kcal mol-1 for each carbonyl group with a strong dependency on the interatomic distances. The rigorous analysis of the electron density in the topological theory of atoms in molecules framework clearly shows that the origin of O-C═O interactions are through the nO → π*C═O electron transfer mechanism. Such interactions are slightly weaker than a canonical hydrogen bond but seemingly stronger than a van der Waals interaction. This interaction must be considered as a stereoelectronic effect due the electronic transfer between the interacting groups, which are limited by their relative stereochemistry and can be represented by a bond-no bond interaction, causing the pyramidalization of the carbonyl, which is the charge acceptor group.

The pair coupled cluster doubles (pCCD) method (where the excitation manifold is restricted to electron pairs) has a series of interesting features. Among others, it provides ground-state energies very close to what is obtained with doubly-occupied configuration interaction (DOCI), but with polynomial cost (compared with the exponential cost of the latter). Here, we address whether this similarity holds for excited states, by exploring the symmetric dissociation of the linear \ce{H4} molecule. When ground-state Hartree-Fock (HF) orbitals are employed, pCCD and DOCI excited-state energies do not match, a feature that is assigned to the poor HF reference. In contrast, by optimizing the orbitals at the pCCD level (oo-pCCD) specifically for each excited state, the discrepancies between pCCD and DOCI decrease by one or two orders of magnitude. Therefore, the pCCD and DOCI methodologies still provide comparable energies for excited states, but only if suitable, state-specific orbitals are adopted. We also assessed whether a pCCD approach could be used to directly target doubly-excited states, without having to resort to the equation-of-motion (EOM) formalism. In our $\Delta$oo-pCCD model, excitation energies were extracted from the energy difference between separate oo-pCCD calculations for the ground state and the targeted excited state. For a set comprising the doubly-excited states of \ce{CH+}, \ce{BH}, nitroxyl, nitrosomethane, and formaldehyde, we found that $\Delta$oo-pCCD provides quite accurate excitation energies, with root mean square deviations (with respect to full configuration interaction results) lower than CC3 and comparable to EOM-CCSDT, two methods with much higher computational cost., Comment: 12 pages, 4 figures

High-resolution transmission electron microscopy results reveal that oriented-attachment- and defect-dependent mechanisms rule the size and shape evolution of the monodispersed PbTe quantum dots (QDs). The former is characterized by the growth of quasi-cubic PbTe QDs, which depends on both the geometric constraints imposed by the {200} facets and the defect-free lattice, while the latter one is a defect-dependent mechanism which gives way to the formation of decahedral PbTe QDs (∼6 nm). Experimentally, formaldehyde is an important parameter for the mechanochemical synthesis of monodispersed PbTe QDs, which has not been studied until now. In a theoretical context, Fukui functions reveal that Pb surface atoms are the most reactive sites toward nucleophilic attacks, and the Lowdin charge analysis shows that formaldehyde molecules tend to donate their electron pairs to Pb atoms. Besides, formaldehyde-molecule-on-PbTe adsorption energies (-4.46 to -21.16 kcal mol-1) agree with ligand-surface polar electrostatic interactions. Based on dispersion-corrected density functional theory calculations, PbTe QDs exhibited decahedral and faceted shapes. According to modified Wulff constructions, the decahedral shape is a result of (111) facets (Δγ = -2.79 meV A-2), whereas the faceted and rounded shapes are due to the interaction of (100), (110), and (111) facets.

Photosynthetic integral membrane reaction center (RC) proteins capture and convert sunlight into chemical energy via efficient charge separation achieved through a series of rapid, photoinitiated electron transfer steps. These fast electron transfers create an entangled spin qubit (radical) pair that contains detailed information about the weak magnetic interactions, structure, and dynamics of localized protein environments involved in charge separation events. Herein, we investigate how these entangled electron spin qubits interact with nuclear spins of the protein environment using the high spectral resolution of 130 GHz electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR). Spectroscopic interrogation enabled the observation and probing of protons located in the electron transfer pathway between the membrane-spanning electron pair P+QA- (where P+ is the primary donor, a special pair of bacteriochlorophylls, and QA is the primary quinone acceptor) in the bacterial RC. Spectroscopic analysis reveals hydrogen-bonding interactions involved in regulating the route that light-induced electrons travel through the RC protein during charge separation.

A three-component Lewis acid-base (Lewis trio) involving a bulky chiral primary amine, B(C6 F5 )3 and a bulky tertiary amine has been developed as an effective enamine catalyst for enantioselective disulfuration reactions. The bulky tertiary amine was found to activate a bulky primary-tertiary diamine-borane Lewis pair for enamine catalysis via frustrated interaction. The resulted chiral bulky Lewis trio (BLT) allows for the construction of chiral disulfides via direct disulfuration with β-ketocarbonyls or α-branched aldehydes in a practical and highly stereocontrolled manner.

The coordination of a carbonyl to a Lewis acid represents the first step in a wide range of catalytic transformations. In many reactions it is necessary for the Lewis acid to discriminate between starting material and product, and as a result, how these structures behave in solution must be characterized. Herein, we report the application of computational modeling to calculate properties of the solution interactions of acetone and benzaldehyde with FeCl(3). Using these chemical models, we can predict spectral features in the carbonyl region of infrared (IR) spectroscopy. These simulated spectra are then directly compared to experimental spectra generated via titration-IR. We observe good agreement between theory and experiment, in that, between 0 and 1 equiv carbonyl with respect to FeCl(3), a pairwise interaction dominates the spectra. When >1 equiv carbonyl is present, our theoretical model predicts two possible structures composed of 4:1 carbonyl to FeCl(3), for acetone as well as benzaldehyde. When these predicted spectra are compared with titration-IR data, both structures contribute to the observed solution interactions. These findings suggest that the resting state of FeCl(3)-catalyzed carbonyl-based reactions employing simple substrates starts as a Lewis pair, but this structure is gradually consumed and becomes a highly ligated, catalytically less active Fe-centered complex as the reaction proceeds. An analytical model is proposed to quantify catalyst inhibition due to equilibrium between 1:1 and 4:1 carbonyl:Fe complexes.

Black orthorhombic (B-γ) CsSnI3 with reduced biotoxicity and environmental impact and excellent optoelectronic properties is being considered as a promising eco-friendly candidate for high-performing perovskite solar cells (PSCs). A major challenge in a large-scale implementation of CsSnI3 PSCs includes the rapid transformation of Sn2+ to Sn4+ (within a few minutes) under an ambient-air condition. Here, we demonstrate that ambient-air stable B-γ CsSnI3 PSCs can be fabricated by incorporating N,N'-methylenebis(acrylamide) (MBAA) into the perovskite layer and by using poly(3-hexylthiophene) as the hole transporting material. The lone electron pairs of -NH and -CO units of MBAA are designed to form coordination bonding with Sn2+ in the B-γ CsSnI3, resulting in a reduced defect (Sn4+) density and better stability under multiple conditions for the perovskite light absorber. After a modification, the highest power conversion efficiency (PCE) of 7.50% is documented under an ambient-air condition for the unencapsulated CsSnI3-MBAA PSC. Furthermore, the MBAA-modified devices sustain 60.2%, 76.5%, and 58.4% of their initial PCEs after 1440 h of storage in an inert condition, after 120 h of storage in an ambient-air condition, and after 120 h of 1 Sun continuous illumination, respectively.

Expanding the optical absorption range of photocatalysts is still a key endeavor in graphitic carbon nitride (g-C3N4) studies. Here, we report on a novel thiophene group extending the optical property, which is assigned to n-π* electronic transitions involving the two lone pairs on sulfur (TLPS). The as-prepared samples, denoted as CN-ThAx (where x indicates the amount of ThA added, mg), showed an additional absorption above 500 nm as compared to pristine g-C3N4. Further, the thiophene group enhanced charge carrier separation to suppress e−/h+ pair recombination. The experimental results suggest that the thiophene group can obstruct the polymerization of melem to generate a large plane, thus exposing the lone electron pairs on the sulfur. The photocatalytic activity was evaluated in the decomposition of bisphenol A and H2 evolution. Compared with g-C3N4, the optimized CN-ThA30 sample led to a 6.6- and 2-fold enhancement of the degradation and H2 generation rates, respectively. The CN-ThA30 sample allowed for synchronous H2 production and BPA decomposition.

A simple method to determine Lewis electron dot structures and formal charges without a need to sum all of the valence electrons, reorganize electron pairs, draw and pair up individual electrons, or remember a formal charge formula is described. The formal charge is determined by the group number (number of valence electrons) and the number of bonds, with the sum of formal charges then being equal to the total charge. This leads directly to a valid Lewis structure. The facility of the procedure allows the student to focus more on the chemical aspects of deciding which valid Lewis structure (or structures) is the correct or most important one.

The space-time ladder theory reveals that the formation of electronic tornadoes, or the formation of electronic dissipative structures, to be precise, the enhancement of electronic Energy Qi field is the basis of superconductivity. The surrounding area of the electronic tornado is expanding, which is the basis of the Meissner effect, and the center is contracting, which is the basis of the pinning force. When the attractive force of the Energy Qi field is greater than the Coulomb repulsive force, the electrons form a Cooper pair and release dark energy into virtual space-time. When the dark energy increases to a certain extent, the virtual space-time frees the Cooper pair and forms an electron-virtual space-time wave, which fluctuates freely in the superconducting material, which is the basis for the superconducting resistance to be zero. This is similar to the principle of a hot air balloon. The virtual space-time is hot air and the electron pair is a hot air balloon device. Conductor electrons are free and easy to emit dark energy, resulting in insufficient dark energy, and it is not easy to form electron-pair virtual space-time waves, so the superconducting critical temperature is very low. This is because the emission coefficient of the conductor is too high. Insulator electrons are not easy to emit dark energy and easily form electron-pair virtual space-time waves. Therefore, the superconducting critical temperature is slightly higher because of the low emission coefficient of the insulator. The solution of the Qi-space-time wave equation, that is, the coherence coefficient, is an important factor in superconductivity. In addition, the conditions under which tornadoes form are also an important basis for superconductivity. Finally, it is emphasized that the coherence coefficient and prevention of dark energy emission are the two most important elements for preparing superconducting materials.

The Mes2 P-C≡C-SiMe3 alkyne reacts with the borane H2 B-Fmes by means of a rare 1,1-hydroboration reaction to give an unsaturated C2 -bridged frustrated P/B-H Lewis pair. Most of its reactions are determined by the presence of the B-H functionality at the FLP function and the activated connecting carbon-carbon double bond. It reduces carbon monoxide to the formyl stage. With nitriles it reacts in an extraordinary way: it undergoes a reaction sequence that eventually results in the formation of a P-substituted dihydro-1,2-azaborole derivative. Several similar examples were found. In one case a P-ylide was isolated that was related to an intermediate of the reaction sequence. It subsequently opened in an alternative way to give an alkenyl borane product.

Clusters (Ih)-(Cd, Hg, Yb)@(Pb12, Sn12), (C5v)-(Ag, Au)@BiPb11, (C5v)-Ag@SbSn11, (D5d)(Ni, Pd, Pt)@Bi2Pb10, (D5d)-Pd@Sb2Sn10, (C3v)-(Pb12, Sn12)·(Pb, Sr, Ba), closo-Bi2Pb10, closo-Bi2Pb4, closo-Sb2Sn4, (Ih)-Bi20, (Ih)-Kr@Bi20, and (Ih)-Ni12Bi20 were studied by the DFT PBE0 method. Structures of (Ih)-(Pb, Sr)@(Pb12, Sn12), (Ih)-Ba@Pb12, (D5d)-(He, Ne)@Bi2Pb10, (C3v)-(Pb12, Sn12)∙Yb, (C5v)-(Pb12, Sn12)∙Hg, (Cs)-BiPb11∙(Ag, Au), (Cs)-SbSn11∙Ag, (Cs)-p-Bi2Pb10∙(Ni, Pd, Pt), and (Cs)-p-Sb2Sn10∙Pd clusters are metastable; structures of (Ih)-Ba@Sn12 and (D5d)-(Ar, Kr, Rn)@Bi2Pb10 are unstable. In the (Ih)-Ni12Bi20 cluster, nickel atoms form η5-bonds with the faces of the Bi20 dodecahedron. In the isomers (D4h)- and (C2v)-(Bi, Sb)2(Pb, Sn)4, 6 orbitals of lone electron pairs and 8 bonding three-center orbitals with populations of 2.00 make up a linearly dependent set of 14 natural orbitals. The oxidation state ΞX is associated with the populations of orthogonal orbitals located outside the X atom.

Carborane Bronsted superacids have proven to be useful reagents in a variety of organic and inorganic synthetic processes. In this work, analogs in which the icosahedral CB11 carborane core is replaced by a CAl11 core are studied using ab initio electronic structure tools. Each so-called caralumane Bronsted acid is formed by adding HF, HCl, or HH to a corresponding caralumane Lewis acid possessing a vacant Al-centered orbital that acts to accept an electron pair from the HF, HCl, or HH. The Lewis acid strengths of the species involved, as measured by their F- ion affinities, are all found to exceed the threshold for labeling them Lewis superacids. Also, the deprotonation Gibbs free energies of the Bronsted acids are found to be small enough for them to be Bronsted superacids. When HF or HCl is bound to a caralumane Lewis acid to form the Bronsted acid, the HF or HCl is bound datively to a single Al atom, and hydrogen bonds can be formed between this molecule's H atom and nearby F or Cl atoms attached to other Al atoms. In contrast, when HH is bound to the Lewis acid to form the Bronsted acid, two novel low-energy structures arise, both of which are Bronsted superacids. One has an essentially intact HH molecule attached to a single Al atom in a η2 fashion. In the other, the HH molecule is heterolytically cleaved to generate a hydride ion that attaches to a single Al atom and a proton that binds in a multicenter manner to other Al atoms. The structures and relative energies of a multitude of such caralumane Lewis and Bronsted superacids are provided and discussed.

Ring-opening copolymerization (ROCOP) of epoxide/anhydride/CO2 for the synthesis of CO2-based copolymers is a promising process, because CO2 is an abundant, nontoxic, and low-cost monomer and has b...

ortho-Substituted and unsymmetrical 9-phospha-triptycenes were synthesizedviatwo synthetic approaches involving densely functionalizedortho-halogenated triarylmethane or phosphine precursors.ortho-Substituents imposed a considerable steric shielding due to the tricyclic cage-shaped structure with the aryl rings p-systems orthogonal to the phosphorus electron pair. A series of Au(i) and Rh(i) complexes were analysed in the solid state to determine Tolman electronic parameters, cone angles and buried volumes of these unprecedented functionalized phosphines. Quantum chemical calculations of electronic and steric descriptors revealed that these cage-shaped phosphines are electron-poor and that single methyl substituent is enough to provide the largest effect on steric shielding reported so far in triarylphosphines. An unsymmetrically substituted 9-phosphatriptycene was resolved by chiral HPLC, opening the avenue towards stableP-chirogenic triarylphosphines with unlimited configurational stability for new catalyst development in asymmetric transition-metal catalysis.

The structural, vibrational and electronic properties of the compressed beta-Sb2O3 polymorph, a.k.a. mineral valentinite, have been investigated in a joint experimental and theoretical study up to 23 GPa. The compressibility of the lattice parameters, unit-cell volume and polyhedral unit volume as well as the behaviour of its Raman- and IR-active modes under compression have been interpreted on the basis of ab initio theoretical simulations. Valentinite shows an unusual compressibility up to 15 GPa with four different pressure ranges, whose critical pressures are 2, 4, and 10 GPa. The pressure dependence of the main structural units, the lack of soft phonons, and the electronic density charge topology address the changes at those critical pressures to isostructural phase transitions of degree higher than 2. In particular, the transitions at 2 and 4 GPa can be ascribed to the changes in the interaction between the stereochemically-active lone electron pairs of Sb atoms under compression. The changes observed above 10 GPa, characterized by a general softening of several Raman- and IR-active modes, point to a structural instability prior to the 1st-order transition occurring above 15 GPa. Above this pressure, a tentative new high-pressure phase (s.g. Pcc2) has been assigned by single-crystal and powder X-ray diffraction measurements., This research was partially supported by the MINECO (FIS2017-83295-P, MAT2016-75586-C4-1/2/3-P, PGC2018- 097520-A-100, RED and PID2019-106383GB-41/42/43), by the MALTA-CONSOLIDER TEAM network (RED2018-102612-T) and by the EU-FEDER. JAS acknowledges the Ramon y Cajal fellowship (RYC-2015-17482) for financial support. VM thanks the Juan de la Cierva Program (FJCI-2016-27291) and Beatriz Galindo Fellowship (BG20/00077) for financial support. We also thank the ALBA (2016091901 experiment) and DIAMOND light source (CY22223 experiment) for providing beamtime, and Mark Warren, Sarah Barnett and Dominik Daisenberger for their help in the single-crystal X-ray diffraction experiment under pressure.

We present the first example of surface-initiated polymerization mediated by Lewis pairs for the synthesis of polymer brushes on planar substrates. The method enables the rapid grafting polymerization from the self-assembled monolayer or surface-attached macroinitiators, furnishing linear polymer brushes and bottle-brush brushes. Both homopolyester and block copolyester brushes can be synthesized via this versatile approach. This work not only opens up new opportunities for the application of Lewis pair-mediated polymerization but also enriches the surface-initiated polymerization on different surfaces.

An unprecedented radical polymerization of various (meth)acrylates, diethyl acrylamide, and 4-vinylpyridine initiated by Lewis pair (LP) catalysts, specifically PPh3/Cu(OTf)2 or PPh3/Sn(OTf)2, is r...

High-pressure single-crystal to 20 GPa and powder diffraction measurements to 50 GPa, show that the structure of Pb2SnO4strongly distorts on compression with an elongation of one axis. A structural phase transition occurs between 10 GPa and 12 GPa, with a change of space group fromPbamtoPnam. The resistivity decreases by more than six orders of magnitude when pressure is increased from ambient conditions to 50 GPa. This insulator-to-semiconductor transition is accompanied by a reversible appearance change from transparent to opaque. Density functional theory-based calculations show that at ambient conditions the channels in the structure host the stereochemically-active Pb 6s2lone electron pairs. On compression the lone electron pairs form bonds between Pb2+ions. Also provided is an assignment of irreducible representations to the experimentally observed Raman bands.

An intramolecular ethylene-bridged PH/BH system, isolated as a dimer, reduces carbon monoxide to the -CH2-O- state. In the presence of B(C6F5)3 the frustrated PH/BH Lewis pair reacts with carbon mo...

Designing crystalline solids in which intrinsically and extremely low lattice thermal conductivity mainly arises from their unique bonding nature rather than structure complexity and/or atomic disorder could promote thermal energy manipulation and utilization for applications ranging from thermoelectric energy conversion to thermal barrier coatings. Here, we report an extremely low lattice thermal conductivity of ∼0.34 W m-1 K-1 at 300 K in the new complex sulfosalt MnPb16Sb14S38. We attribute the ultralow lattice thermal conductivity to a synergistic combination of scattering mechanisms involving (1) strong bond anharmonicity in various structural building units, owing to the presence of stereoactive lone-electron-pair (LEP) micelles and (2) phonon scattering at the interfaces between building units of increasing size and complexity. Remarkably, low-temperature heat capacity measurement revealed a Cp value of 0.206 J g-1 K-1 at T > 300 K, which is 22% lower than the Dulong-Petit value (0.274 J g-1 K-1). Further analysis of the Cp data and sound velocity (ν = 1834 m s-1) measurement yielded Debye temperature values of 161 and 187 K, respectively. The resulting Gruneisen parameter, γ = 1.65, further supports strong bond anharmonicity as the dominant mechanism responsible for the observed extremely low lattice thermal conductivity.

Despite the abundance of data concerning single-photon double ionization of methanol, the spin state of the emitted electron pair has never been determined. Here we present the first evidence that identifies the emitted electron pair spin as overwhelmingly singlet when the dication forms in low-energy configurations. The experimental data show that while the yield of the CH2O+ + H3+ Coulomb explosion channel is abundant, the metastable methanol dication is largely absent. According to high-level ab initio simulations, these facts indicate that photoionization promptly forms singlet dication states, where they quickly decompose through various channels, with significant H3+ yields on the low-lying states. In contrast, if we assume that the initial dication is formed in one of the low-lying triplet states, the ab initio simulations exhibit a metastable dication, contradicting the experimental findings. Comparing the average simulated branching ratios with the experimental data suggests a >3 order of magnitude enhancement of the singlet:triplet ratio compared with their respective 1:3 multiplicities.

Because of a charge-dipole interaction involving nonbonding electron pairs on fluorine, protonation of trifluoromethyl allenes leads to tri- or tetrasubstituted alkenes with high (Z)-selectivity. T...

Actualmente resulta inherente la obtención de energía de fuentes alternas y renovables, dentro de estas, la energía solar se posiciona firmemente como una de las principales opciones para dar solución a esta problemática. La tercera generación de celdas solares, las sensibilizadas con colorante (DSSC), ofrece un amplio campo de oportunidad para la investigación. En este trabajo, se analiza el efecto, en el rendimiento de la celda, de la modificación estructural del semicondutor (TiO2) y el dopaje con Neodimio. En tanto al semiconductor se optó por llevar a cabo la síntesis del mismo sobre el vidrio conductor (FTO), que posteriormente conformaría el foto-ánodo, con una estructura unidimensional (nano-varillas cristalinas de dióxido de titanio en fase rutilo), recientes publicaciones han reportado las ventajas para transportar los electrones de las mismas. Se ha decidido dopar las varillas con un elemento del grupo de los lantánidos, el Neodimio, teniendo dos propósitos, por una parte, aumentar la inyección de electrones excitados, y de igual forma, disminuir la tasa de recombinación del par electrón hueco dentro de la celda.

In order to study electrically and magnetically charged vortices in fractional quantum Hall effect and anyonic superconductivity, the Maxwell–Chern–Simons (MCS) model was introduced by Lee et al. (Phys Lett B 252:79–83, 1990) as a unified system of the classical Abelian–Higgs model (AH) and the Chern–Simons (CS) model. In this article, the first goal is to obtain the uniform (CS) limit result of (MCS) model with respect to the Chern–Simons parameter, without any restriction on either a particular class of solutions or the number of vortex points, as the Chern–Simons mass scale tends to infinity. The most important step for this purpose is to derive the relation between the Higgs field and the neutral scalar field. Our (CS) limit result also provides the critical clue to answer the open problems raised by Ricciardi and Tarantello (Comm Pure Appl Math 53:811–851, 2000) and Tarantello (Milan J Math 72:29–80, 2004), and we succeed to establish the existence of periodic Maxwell–Chern–Simons vortices satisfying the concentrating property of the density of superconductive electron pairs. Furthermore, we expect that the (CS) limit analysis in this paper would help to study the stability, multiplicity, and bubbling phenomena for solutions of the (MCS) model.

The geminal frustrated Lewis pair (F5C2)3SnCH2P(tBu)2 (1) reacted with N‐sulfinylaniline PhNSO to afford the first sulfur monoxide adduct of a main group metal, (F5C2)3SnCH2P(tBu)2⋅SO (2), which contains a SnCPSO ring. The second product is a phenylnitrene adduct of 1. The surprising stability of 2 was compared with the stabilities of the so far inaccessible O2 and S2 adducts of 1. Attempts to prepare these from 1 and the elemental chalcogens (O2, S8, Se∞, Te∞) led to four‐membered SnCPE ring systems. Quantum‐chemical investigations of 2 demonstrate the bond polarity of the SO unit to stabilize 2., The first adduct of SO to a main group metal system was found by reacting PhNSO with an intramolecular Sn/P frustrated Lewis pair; the exceptional stability of the adduct is attributed to the polarity of the incorporated SO unit.

A new interpretation of the emission properties of carbon nanotubes is presented using the theory of electron conjugation. The presence of emission molecular states in the energy spectrum of carbon nanotubes, characterized by specific localization of electron density on the end surfaces of carbon nanotubes, is explained from the viewpoint of the concepts of in-plane and ρ-electron conjugation. Based on an analysis of the behavior of emission molecular orbitals in a constant electric field, it is concluded that such localization of electron density is the physical basis for electron emission. It is established that this approach describes known experimental and theoretical results well and can be used to predict the emission properties of a wide range of objects.

Ten years have passed since the conception of what was termed Lewis pair polymerization (LPP) that employs Lewis acid and base in pairs to not only activate monomers but also effect chain initiatio...

Doppler ­ broadening spectroscopy is a technique that is used to know the properties of matter by means of gamma quanta. The entire energy of an annihilation positron – electron pair includes the energy according to its mass (= 2 x 511 Kev) and kinetic energy corresponding to the motion of the particles causes an energy shift of the annihilation line. The line shape has two parameters S and W parameters,but the W parameter is more sensitive to the chemical surrounding of the annihilation site than the S parameter, because the core electron having high momentum are contributing. Mainlyin the region of large deviations from the annihilation energy of 511 kev. Both the S and w parameter are sensitive to the concentration and kind of defect.The goal of our work is to investigate the dependence of annihilation parameters on crystal defect the content of Mg atoms in a series of commercial Al – alloys by Doppler broadening technique . Position parameter like (crystallite size – trapping rate – defect density – dislocation density Storedenergy).

Using ab initio electronic structure methods with flexible atomic orbital basis sets, we examined the nature of the bonding arising from donation of an ns2 electron pair on an alkaline earth atom (Mg or Ca) into a vacant n'p orbital on the group 13 atom of BH3, AlH3, or GaH3. We also examined what happens when an excess electron is attached to form corresponding molecular anions. Although the geometries of MgBH3, MgAlH3, MgGaH3, and CaBH3 are found to be much as one would expect for datively bound molecules, CaAlH3 and CaGaH3 were found to have very unusual geometries in that their Al-H or Ga-H bonds are directed toward the Ca atom rather than away, as in the other compounds. Internal electrostatic Coulomb attractions between the partially positively charged Ca center and the partially negatively charged H centers were suggested as a source of these unusual geometries. The other novel finding is that the electron affinities (EAs) of all six M'-MH3 species lie in the 0.7-1.0 eV range, which is suggestive of ionic electronic structures for the neutrals even though the partial charges on the alkaline earth centers are as low as 0.3 atomic units. Partial positive charge on the alkaline earth atoms combined with substantial electron affinities of the BH3, AlH3, and GaH3 groups, but only when distorted from planar geometries, were suggested to be the primary contributors to the large EAs.