Four-electron Bonds Research Articles

Computational insights into three-centre four-electron bridging hydride bond in boryl type PBP-M dihydride complexes

Computational insights into three-centre four-electron bridging hydride bond in boryl type PBP-M dihydride complexes

Triply Bonded Pancake π-Dimers Stabilized by Tetravalent Actinides.

Aromatic π-stacking is a weakly attractive, noncovalent interaction often found in biological macromolecules and synthetic supramolecular chemistry. The weak nondirectional nature of π-stacking can present challenges in the design of materials owing to their weak, nondirectional nature. However, when aromatic π-systems contain an unpaired electron, stronger attraction involving face-to-face π-orbital overlap is possible, resulting in covalent so-called "pancake" bonds. Two-electron, multicenter single pancake bonds are well known, whereas four-electron double pancake bonds are rare. Higher-order pancake bonds have been predicted, but experimental systems are unknown. Here, we show that six-electron triple pancake bonds can be synthesized by a 3-fold reduction of hexaazatrinaphthylene (HAN) and subsequent stacking of the [HAN]3- triradicals. Our analysis reveals a multicenter covalent triple pancake bond consisting of a σ-orbital and two equivalent π-orbitals. An electrostatic stabilizing role is established for the tetravalent thorium and uranium ions in these systems. We also show that the electronic absorption spectrum of the triple pancake bonds closely matches computational predictions, providing experimental verification of these unique interactions. The discovery of conductivity in thin films of triply bonded π-dimers presents new opportunities for the discovery of single-component molecular conductors and other spin-based molecular materials.

Halogen Bonds of Halogen(I) Ions─Where Are We and Where to Go?

Halenium ions, X+, are particularly strong halogen-bond donors that interact with two Lewis bases simultaneously to form linear [D···X···D]+-type halonium complexes. Their three-center, four-electron halogen bond is both fundamentally interesting and technologically valuable as it tames the reactivity of halogen(I) ions, opening up new horizons in a variety of fields including synthetic organic and supramolecular chemistry. Understanding this bonding situation enables the development of improved halogen(I) transfer reactions and of advanced functional materials. Following a decade of investigations of basic principles, the range of applications is now rapidly widening. In this Perspective, we assess the status of the field and identify its key advances and the main bottlenecks. Clearing common misunderstandings that may hinder future progress, we aim to inspire and direct future research efforts.

Enhancement of Near-Infrared Emission Based on Hypervalent Germanium(IV)-Fused Azobenzene Compounds with Electron-Donating Groups

Abstract NIR-light emitting materials are significant as a source for NIR-light technology. Previously, we have found that hypervalent germanium-fused azobenzene (GAz) compounds showed NIR emissions despite the small π-conjugated systems owing to trigonal bipyramidal geometry with three-center four-electron (3c-4e) bonds. Herein, we succeed in enhancing their luminescence properties by introduction of electron-donating groups. It is revealed that the frontier molecular orbitals of the π-conjugated systems with the hypervalent bonds can be varied depending on the type of substituents. As a result, a GAz compound with diphenylamine groups shows efficient NIR emission at room temperature (λPL = 761 nm and ΦPL = 0.07) and at 77 K (λPL = 749 nm and ΦPL = 0.20). Furthermore, data from theoretical calculations support the experimental results and provide additional information on the producibility of the hypervalent compounds. Our findings afford strategies to expand the library of the fine-tunable NIR-luminescent materials involving heteroatoms.

Near-Infrared Emissive Hypervalent Compounds with Germanium(IV)-Fused Azobenzene π-Conjugated Systems.

A novel molecular design for showing near-infrared (NIR) emission is still required for satisfying growing demands for NIR-light technology. In this research, hypervalent compounds with germanium (Ge)-fused azobenzene (GAz) scaffolds were discovered that can exhibit NIR emission (λPL =690∼721 nm, ΦPL =0.03∼0.04) despite compact π-conjugated systems. The unique optical properties are derived from the trigonal bipyramidal geometry of the hypervalent compounds constructed by combination of Ge and azobenzene-based tridentate ligands. Experimental and theoretical calculation results disclosed that the germanium-nitrogen (Ge-N) coordination at the equatorial position strongly reduces the energy level of the LUMO (lowest unoccupied molecular orbital), and the three-center four-electron (3 c-4 e) bond in the apical position effectively rises the energy level of the HOMO (highest occupied molecular orbital). It is emphasized that large narrowing of the HOMO-LUMO energy gap is achieved just by forming the hypervalent bond. In addition, the narrow-energy-gap property can be enhanced by extension of π-conjugation. The obtained π-conjugated polymer shows efficient NIR emission both in solution (λPL =770 nm and ΦPL =0.10) and film (λPL =807 nm and ΦPL =0.04). These results suggest that collaboration of a hypervalent bond and a π-conjugated system is a novel and effective strategy for tuning electronic properties even in the NIR region.

Intramolecular hydrogen bonding analysis.

The quasi-atomic orbital (QUAO) bonding analysis is used to study intramolecular hydrogen bonding (IMHB) in salicylic acid and an intermediate that is crucial to the synthesis of aspirin. The bonding analysis rigorously explores IMHB through directly accessing information that is intrinsic to the molecular wave function, thereby bypassing the need for intrinsically biased methods. The variables that affect the strength of IMHB are determined using kinetic bond orders, QUAO populations, and QUAO hybridizations. Important properties include both the interatomic distance between hydrogen and oxygen participating in the IMHB and the hybridization on the oxygen. The bonding analysis further shows that each intramolecular hydrogen bond is a four-electron three-center bond. The bonding analysis is used to understand how aromatic reactivity changes due to the effect of functional groups on the aromatic ring.

Long-bonding and bonding nature in noble gas insertion compounds MNgBY of transition metal-boron bond

The nature of inert gas bonding has always been an important topic. The bonds of noble gases cover the entire range of chemical bonds, from the weakest van der Waals forces, to non-covalent interactions, and to covalent bonds. Two types of methods were used to investigate the properties of chemical bonds in the inert gas inserted compound MNgBY with the transition metal M = Cu/Ag/Au and substituents Y = O/S/NH, one based on orbital analysis and the other based on electron density analysis. The NBO/NRT analysis shows that in these compounds there exists long-bonding striding the noble gas between the transitional metal and boron, similar to the noble gas insertion compounds HNgX of hydrohalide, and so a three-center four-electron bond exists among the M-Ng-B part. The electron density analyses show that the M-Ng bond between the metal Cu/Ag/Au and noble gas and the Ng-B bond in the Cu/Ag compounds are partial covalent but the Ng-B bond in Au compounds is a typical covalent bond. The large relativistic effects of Au cause the bonds in Au compounds shorter and stronger than the bonds in Ag/Cu compounds. The properties of the M-Ng and Ng-B bonds are not affected by substituents Y, but the bond lengths are sensitive to substituents.

PPV-type π-conjugated polymers based on hypervalent tin(IV)-fused azobenzene complexes showing near-infrared absorption and emission

We demonstrate near-infrared (NIR) absorptive and emissive poly(p-phenylene vinylene) (PPV)-type π-conjugated polymers based on hypervalent tin-fused azobenzene (TAz) complexes. Taking advantage of the inherent narrow-energy gap of TAz complexes originating from the three-center four-electron (3c-4e) bond and nitrogen–tin (N–Sn) coordination, the synthesized polymers, TAz-PPVs, showed absorption, and emission in wavelength regions of >750 and 810 nm in diluted solution, respectively. From the experimental and theoretical investigations, the elevation of the highest occupied molecular orbital (HOMO) and the reduction of the lowest unoccupied molecular orbital (LUMO) were simultaneously shown to be caused by the extension of π-conjugation. The effective conjugation length was calculated to be n > 10 (n: degree of polymerization), and the value was comparable to conventional PPV systems. Through this research, we revealed that π-conjugated systems including hypervalent bonds were able to expand π-conjugation. According to the concept of “element blocks”, the development of heteroatom-containing narrow-energy-gap monomers should be a novel approach for the construction of new NIR-absorptive and emissive bland materials.

Vapochromic Luminescent π-Conjugated Systems with Reversible Coordination-Number Control of Hypervalent Tin(IV)-Fused Azobenzene Complexes.

The dynamic and reversible changes of coordination numbers between five and six in solution and solid states, based on hypervalent tin(IV)-fused azobenzene (TAz) complexes, are reported. It was found that the TAz complexes showed deep-red emission owing to the hypervalent bond composed of an electron-donating three-center four-electron (3c-4e) bond and an electron-accepting nitrogen-tin (N-Sn) coordination. Furthermore, hypsochromic shifts in optical spectra were observed in Lewis basic solvents because of alteration of the coordination number from five to six. In particular, vapochromic luminescence was induced by attachment of dimethyl sulfoxide (DMSO) vapor to the coordination point at the tin atom accompanied with a crystal-crystal phase transition. Additionally, the color-change mechanism and degree of binding constants were well explained by theoretical calculation. To the best of our knowledge, this is the first example of vapochromic luminescence by using stable and variable coordination numbers of hypervalent bonds.

A “nucleophilic” iodine in a halogen-bonded iodonium complex manifests an unprecedented I+···Ag+ interaction

Summary When an electron is removed from a halogen atom, it forms a halenium ion X+ (X = I, Br, Cl). In halogen bonding (XB), X+ is considered as a strong XB donor, and when interacting with two XB acceptors (e.g., pyridine), it forms a halonium XB complex with a [N–I–N] three-center-four-electron bond with the two XB acceptors. An unprecedented I+···Ag+ interaction occurs between a [L1–I–L1]+ halogen-bonded complex and a [L2–Ag–L2]+ complex in which the iodonium ion acts like a nucleophile and donates electrons to the silver(I) cation. The X-ray diffraction analysis reveals a short contact [3.4608(3) A] between the I+ and Ag+ cations, and ITC measurements give a ΔG of −6.321 kcal/mol and Ka∼37,000 M−1 for the 1:1 complex. The DFT computational study on the nature of the I+···Ag+ interaction indicates that the I+ is nucleophilic in character, manifesting an unusual and strongly attractive interaction between the I+ and Ag+ cations.

Synthesis and Characterization of Monomeric Hexacoordinated Chalcogenonium Salts Bearing 2-(2-Pyridyl)phenyl Ligands

Abstract Consecutive treatment of 2-(2-lithiophenyl)pyridine with chalcogen tetrachlorides (ChCl4; Ch = Se and Te) and KPF6 afforded the hexafluorophosphate salts of tris[2-(2-pyridyl)phenyl]selenonium [(ppy)3Se]+ ([1]+) and tris[2-(2-pyridyl)phenyl]telluronium [(ppy)3Te]+ ([2]+), respectively. The chalcogenonium salts [1][PF6] and [2][PF6] exhibit extremely high thermal stability and high melting points. Their solid-state structures revealed distorted octahedral bonding geometries with a C3-symmetrical facial configuration. Quantum chemical calculations on [1]+ and [2]+ strongly suggest that their HOMO−3s involve lone pairs of electrons (LPs) on the central chalcogen atoms, and that the three Ch–N (Ch = Se and Te) bonds are formed by LP(N)→σ*(Ch–C) donor-acceptor interactions. Based on theoretical calculations and 77Se and 125Te NMR spectral data, the C–Ch–N moieties of [1]+ and [2]+ were characterized as asymmetrical three-center four-electron σ-type bonds [σ(3c–4e)]. Both organochalcogenonium salts represent novel monomeric hexacoordinated species that bear 14 formal valence electrons (14–Se–6 and 14–Te–6, respectively). A quantum theory of atoms-in-molecules dual functional analysis predicted that the C–Ch interaction of the σ(3c–4e) C–Ch–N moiety (Ch = Se and Te) is weakly covalent, while the Se–N and Te–N interactions were predicted to have the typical characteristics of hydrogen bonds and molecular complexes, respectively. The differences between [2][PF6] and the recently reported [2][Br] were also carefully examined.

Revisiting the covalent nature of halogen bonding: a polarized three-center four-electron bond.

As an important intermolecular interaction, halogen bonding has been studied extensively, but its nature still suffers from controversy without one uniform essence. Electrostatics, charge transfer, polarization and dispersion are emphasized, but the covalent nature is usually overlooked except for the strong halogen bonding species I3−, which is widely accepted as a result of a three-center four-electron (3c-4e) interaction. In our study, the potential energy surface of I3− has been evaluated to explore the dissociation from I3− to I2⋯I−. We found that different from an equivalent 3c-4e bond in I3−, I2⋯I− can be rationalized by a polarized one. In addition, when the orbitals are polarized, it is exactly what traditional charge transfer or the popular σ-hole picture describes. I3− can be described by the Lewis theory model with the middle I+ cation serving as the Lewis acid and two terminal I− anions acting as Lewis base. Therefore, we further extended this model to a series of I-containing species with chemical composition of L–I+–L, F−–I+–L and H3P–I+–L (L = OH−, F−, Cl−, Br−, I−, PH3, NH3, H2S, HI, H2O, HBr and HCl) to explore the nature of halogen bonding. When the forces of two bases around I+ are the same, it corresponds to an equivalent 3c-4e bond, such as I3−. Otherwise, it is a polarized multicenter bond, such as I2⋯I−. This work gives a new insight into the nature of halogen bonding compounds: besides the well-known I3−, the nature of the other species is also a multicenter bond, existing as equivalent and polarized 3c-4e bonds, respectively.

Halogen Bond of Halonium Ions: Benchmarking DFT Methods for the Description of NMR Chemical Shifts.

Because of their anisotropic electron distribution and electron deficiency, halonium ions are unusually strong halogen-bond donors that form strong and directional three-center, four-electron halogen bonds. These halogen bonds have received considerable attention owing to their applicability in supramolecular and synthetic chemistry and have been intensely studied using spectroscopic and crystallographic techniques over the past decade. Their computational treatment faces different challenges to those of conventional weak and neutral halogen bonds. Literature studies have used a variety of wave functions and DFT functionals for prediction of their geometries and NMR chemical shifts, however, without any systematic evaluation of the accuracy of these methods being available. In order to provide guidance for future studies, we present the assessment of the accuracy of 12 common DFT functionals along with the Hartree–Fock (HF) and the second-order Møller–Plesset perturbation theory (MP2) methods, selected from an initial set of 36 prescreened functionals, for the prediction of 1H, 13C, and 15N NMR chemical shifts of [N–X–N]+ halogen-bond complexes, where X = F, Cl, Br, and I. Using a benchmark set of 14 complexes, providing 170 high-quality experimental chemical shifts, we show that the choice of the DFT functional is more important than that of the basis set. The M06 functional in combination with the aug-cc-pVTZ basis set is demonstrated to provide the overall most accurate NMR chemical shifts, whereas LC-ωPBE, ωB97X-D, LC-TPSS, CAM-B3LYP, and B3LYP to show acceptable performance. Our results are expected to provide a guideline to facilitate future developments and applications of the [N–X–N]+ halogen bond.

Symmetry of Three-Center, Four-Electron Bonds

Symmetry of Three-Center, Four-Electron Bonds

Symmetry of three-center, four-electron bonds.

Three-center, four-electron bonds provide unusually strong interactions; however, their nature remains ununderstood. Investigations of the strength, symmetry and the covalent versus electrostatic character of three-center hydrogen bonds have vastly contributed to the understanding of chemical bonding, whereas the assessments of the analogous three-center halogen, chalcogen, tetrel and metallic Created by potrace 1.16, written by Peter Selinger 2001-2019 ]]> -type long bonding are still lagging behind. Herein, we disclose the X-ray crystallographic, NMR spectroscopic and computational investigation of three-center, four-electron [D–X–D]+ bonding for a variety of cations (X+ = H+, Li+, Na+, F+, Cl+, Br+, I+, Ag+ and Au+) using a benchmark bidentate model system. Formation of a three-center bond, [D–X–D]+ is accompanied by an at least 30% shortening of the D–X bonds. We introduce a numerical index that correlates symmetry to the ionic size and the electron affinity of the central cation, X+. Providing an improved understanding of the fundamental factors determining bond symmetry on a comprehensive level is expected to facilitate future developments and applications of secondary bonding and hypervalent chemistry.

O-I-O halogen bond of halonium ions.

The reactivity of halonium ions is conveniently modulated by three-center, four-electron halogen bonds. Such stabilized halonium complexes are valuable reagents for oxidations and halofunctionalization reactions. We report the first example of the stabilization of a halenium ion in a three-center, four-electron halogen bond with two oxygen ligands. The influence of electron density and solvent on the stability of the complexes is assessed. O-I-O halogen bond complexes are applicable as synthetic reagents and as supramolecular synthons.

A Continuum from Halogen Bonds to Covalent Bonds: Where Do λ3 Iodanes Fit?

The intrinsic bonding nature of λ 3 -iodanes was investigated to determine where its hypervalent bonds fit along the spectrum between halogen bonding and covalent bonding. Density functional theory with an augmented Dunning valence triple zeta basis set ( ω B97X-D/aug-cc-pVTZ) coupled with vibrational spectroscopy was utilized to study a diverse set of 34 hypervalent iodine compounds. This level of theory was rationalized by comparing computational and experimental data for a small set of closely-related and well-studied iodine molecules and by a comparison with CCSD(T)/aug-cc-pVTZ results for a subset of the investigated iodine compounds. Axial bonds in λ 3 -iodanes fit between the three-center four-electron bond, as observed for the trihalide species IF 2 − and the covalent FI molecule. The equatorial bonds in λ 3 -iodanes are of a covalent nature. We explored how the equatorial ligand and axial substituents affect the chemical properties of λ 3 -iodanes by analyzing natural bond orbital charges, local vibrational modes, the covalent/electrostatic character, and the three-center four-electron bonding character. In summary, our results show for the first time that there is a smooth transition between halogen bonding → 3c–4e bonding in trihalides → 3c–4e bonding in hypervalent iodine compounds → covalent bonding, opening a manifold of new avenues for the design of hypervalent iodine compounds with specific properties.

Carbon’s Three-Center, Four-Electron Tetrel Bond, Treated Experimentally

Tetrel bonding is the noncovalent interaction of group IV elements with electron donors. It is a weak, directional interaction that resembles hydrogen and halogen bonding yet remains barely explored. Herein, we present an experimental investigation of the carbon-centered, three-center, four-electron tetrel bond, [N-C-N]+, formed by capturing a carbenium ion with a bidentate Lewis base. NMR-spectroscopic, titration-calorimetric, and reaction-kinetic evidence for the existence and structure of this species is reported. The studied interaction is by far the strongest tetrel bond reported so far and is discussed in comparison with the analogous halogen bond. The necessity of the involvement of a bidentate Lewis base in its formation is demonstrated by providing spectroscopic and crystallographic evidence that a monodentate Lewis base induces a reaction rather than stabilizing the tetrel bond complex. A vastly decreased Lewis basicity of the bidentate ligand or reduced Lewis acidity of the carbenium ion weakens-or even prohibits-the formation of the tetrel bond complex, whereas synthetic modifications facilitating attractive orbital overlaps promote it. As the geometry of the complex resembles the SN2 transition state, it provides a model system for the investigation of fundamental reaction mechanisms and chemical bonding theories.

Force constant decomposition for penta-coordinated XH3 Cl2- (X = C, Si, Ge) structures.

Based on the energy decomposition analysis of an interacting system, we propose a method for force constant decomposition analysis with respect to the specific normal coordinate. Using the presented method, we examined the penta-coordinated XH3Cl2- system (X = C, Si, Ge), which possesses a three-center four-electron bond. The origin of the difference in the stability of the penta-coordinated D3h structures was clearly shown to be the effect of electron delocalization-polarization term. © 2018 Wiley Periodicals, Inc.

Quasi-Atomic Bonding Analysis of Xe-Containing Compounds.

The origin of bonding in the rare-gas-containing molecules HXeCCH, HXeCCXeH, and HXeOXeH is explored using a quasi-atomic orbital (QUAO) analysis. The QUAOs provide qualitative and quantitative data about bonding through transformations of the density matrix. Bond orders, kinetic bond orders, and the extent of transfer of charge are analyzed. Localized molecular orbitals formed from the QUAOs provide additional insights about the relative polarity of bonds formed by xenon. The analysis suggests significant covalent bonding for Xe-Y (Y = C, O) as well as Xe-H, with both bonds using the same pσ-type orbital on Xe. These covalent interactions are established by substantial charge shifts from Xe to Y as well as to H. Accordingly, a covalent three-center four-electron bond links the atoms H-Xe-Y. On the basis of the analysis, electrostatic interactions do not play a significant role in the Xe-Y or Xe-H bonding.