Single Covalent Bond Research Articles

Sr2B8: A new member to the [formula omitted] and π double aromaticity

In this paper, we have employed the CALYPSO method to perform structure search on the Sr2Bn0/− (n = 1–12) clusters, resulting in the determination of the global energy minimum structures. Moreover, we have conducted PES simulations on each of the obtained structures with the aim of comparing them to experimental data. Upon comparison, we have identified a relatively more stable inverse sandwich structure Sr2B8, and have conducted an analysis of its internal atomic bonding characteristics. The results indicate that there is a significant transfer of valence electrons from the Sr atoms to the B atoms, leading to the occupied orbitals being predominantly contributed by the valence shell of the B atoms. The B atoms are interconnected by covalent single bonds to form a ring structure, with the two Sr atoms positioned on either side of the B ring, binding to the ring through ionic bonds. The entire Sr2B8 exhibits double aromaticity by the delocalized σ occupied orbitals and the delocalized π occupied orbitals.

Prediction of Covalent Metal-Metal Bonding in Cp-M-M'-Nacnac Complexes of Group 2 and 12 Metals (Be, Mg, Ca, Zn, Cd, Hg).

Bimetallic CpMM'Nacnac molecules with group 2 and 12 metals (M=Be, Mg, Ca, Zn, Cd, Hg) that contain novel metal-metal bonding have been investigated in a theoretical study of their molecular and electronic structure, thermodynamic stability, and metal-metal bonding. In all cases the metal-metal bonds are characterized as electron-sharing covalent single bonds from natural bond orbital (NBO) and energy-decomposition analysis with natural orbitals of chemical valence (EDA-NOCV) analysis. The sum of [MM'] charges is relatively constant, with all complexes exhibiting a [MM']2+ core. Quantum theory of atoms in molecules (QTAIM) analysis indicates the presence of non-nuclear attractors (NNA) in the metal-metal bonds of the BeBe, MgMg, and CaCa complexes. There is substantial electron density (0.75-1.33 e) associated with the NNAs, which indicates that these metal-metal bonds, while classified as covalent electron-sharing bonds, retain significant metallic character that can be associated with reducing reactivity of the complex. The predicted stability of these complexes, combined with their novel covalent metal-metal bonding and potential as reducing agents, make them appealing targets for the synthesis of new metal-metal bonds.

Applicability of the Zintl Concept to Understanding the Crystal Chemistry of Lithium-Rich Germanides and Stannides.

With this contribution, we take a new, critical look at the structures of the binary phases Li5Ge2 and Li5Sn2. Both are isostructural (centrosymmetric space group R3̅m, no. 166), and in their structures, all germanium (tin) atoms are dimerized. Application of the valence rules will require the allocation of six additional valence electrons per [Ge2] or [Sn2] unit considering single covalent bonds, akin to those in the dihalogen molecules. Alternatively, four additional valence electrons per [Ge2] or [Sn2] anion will be needed if homoatomic double bonds exist, in an analogy with dioxygen. Therefore, five lithium atoms in one formula unit cannot provide the exact number of electrons, leaving open questions as to what is the nature of the chemical bonding within these moieties. Additionally, by means of single-crystal X-ray diffraction, synchrotron powder X-ray diffraction, and neutron powder diffraction, we established that the Li and Sn atoms in Li5Sn2 are partially disordered, i.e., the actual chemical formula of this compound is Li5-xSn2+x (0 < x < 0.1). The convoluted atomic bonding in the case where tin atoms partially displace lithium atoms results in the formation of larger covalently bonded fragments. Our first-principle calculations suggest that such disorder leads to electron doping. Contrary to that, both experimental and computational findings indicate that in the Li5Ge2 structure, the [Ge2] dimers are slightly oxidized, i.e., hole-doped, as a result of approximately 30% vacancies on a Li site, i.e., the actual chemical formula of this compound is Li5-xGe2 (x ≈ 0.3).

Photouranium-Catalyzed C-F Activation Hydroxylation via Water Splitting.

The C-F bond is the strongest covalent single bond (126 kcal/mol) in carbon-centered bonds, in which the highest electronegativity of fluorine (χ = 4) gives rise to the shortest bond length (1.38 Å) and the smallest van der Waals radius (rw = 1.47 Å), resulting in enormous challenges for activation and transformation. Herein, C-F conversion was realized via photouranium-catalyzed hydroxylation of unactivated aryl fluorides using water as a hydroxyl source to deliver multifunctional phenols under ambient conditions. The activation featured cascade sequences of single electron transfer (SET)/hydrogen atom transfer (HAT)/oxygen atom transfer (OAT), highly integrated from the excited uranyl cation. The *UO22+ prompted water splitting under mild photoexcitation, caging the active oxygen in a peroxo-bridged manner for the critical OAT process and releasing hydrogen via the HAT process.

Thorium(IV)-antimony complexes exhibiting single, double, and triple polar covalent metal-metal bonds.

There is continued burgeoning interest in metal-metal multiple bonding to further our understanding of chemical bonding across the periodic table. However, although polar covalent metal-metal multiple bonding is well known for the d and p blocks, it is relatively underdeveloped for actinides. Homometallic examples are found in spectroscopic or fullerene-confined species, and heterometallic variants exhibiting a polar covalent σ bond supplemented by up to two dative π bonds are more prevalent. Hence, securing polar covalent actinide double and triple metal-metal bonds under normal experimental conditions has been a fundamental target. Here we exploit the protonolysis and dehydrocoupling chemistry of the parent dihydrogen-antimonide anion, to report one-, two- and three-fold thorium-antimony bonds, thus introducing polar covalent actinide-metal multiple bonding under normal experimental conditions between some of the heaviest ions in the periodic table with little or no bulky-substituent protection at the antimony centre. This provides fundamental insights into heavy element multiple bonding, in particular the tension between orbital-energy-driven and overlap-driven covalency for the actinides in a relativistic regime.

Simultaneous identification of strong and weak interactions with Pauli energy, Pauli potential, Pauli force, and Pauli charge.

Strong and weak interatomic interactions in chemical and biological systems are ubiquitous, yet how to identify them on a unified theoretical foundation is still not well established. Recently, we proposed employing Pauli energy-based indexes, such as strong covalent interaction and bonding and noncovalent interaction indexes, in the framework of density functional theory for the purpose. In this work, we extend our previous theoretical work by directly employing Pauli energy, Pauli potential, Pauli force, and Pauli charge to simultaneously identify both strong covalent bonding and weak noncovalent interactions. Our results from this work elucidate that using their signature isosurfaces, we can identify different types of interactions, either strong or weak, including single, double, triple, and quadruple covalent bonds, ionic bond, metallic bond, hydrogen bonding, and van der Waals interaction. We also discovered strong linear correlations between Pauli energy derived quantities and different covalent bond orders. These qualitative and quantitative results from our present study solidify the viewpoint that a unified approach to simultaneously identify both strong and weak interactions is possible. In our view, this work signifies one step forward towards the goal of establishing a density-based theory of chemical reactivity in density functional theory.

Anodic HfO2 crossbar arrays for hydroxide-based memristive sensing in liquids

The development of miniaturized and portable sensing devices is crucial to meeting the high processing capacity demands of contemporary computing systems. Hence, the conceptualization of memristive sensors for hydroxide-containing liquids is proposed in this study. Metal-insulator-metal (MIM) structures were formed on electrochemically anodized Hf thin films with Pt patterned as top electrodes. These MIM memristive structures were integrated into a crossbar array, allowing the investigation of a high number of potential memristor sensors. The MIM structures have demonstrated sensing possibilities in the detection of the hydroxyl ion in D-glucose, used as a standard solution. The sensing method was based on the resistive state ratio extracted from I-U sweeps measurements. Analytical characterization of the memristor sensor was done based on the resistive state ratio in relation to different concentrations of a standard solution drop cast directly on the surface of the device. Linearity was found for D-glucose concentrations ranging from 10 mM to 80 mM with a reasonable corresponding correlation factor (R2=0.96809). Additionally, D-glucose incorporation in anodic oxide was studied by XPS to investigate its effect on conductive filaments formation. A carbon bonded by a single covalent bond to oxygen (O-C-O) was detected, confirming the proposed sensing mechanism defined by the glucose penetrating the oxide/electrode interface.

An Inbuilt Electronic Pawl Gates Orbital Information Processing and Controls the Rotation of a Double Ratchet Rotary Motor.

A direct external input energy source (e.g., light, chemical reaction, redox potential, etc.) is compulsory to supply energy to rotary motors for accomplishing rotation around the axis. The stator leads the direction of rotation, and a sustainable rotation requires two mutual input energy supplies (e.g., light and heat, light and pH or metal ion, etc.); however, there are some exceptions (e.g., covalent single bond rotors and/or motors). On the contrary, our experiment suggested that double ratchet rotary motors (DRMs) can harvest power from available thermal noise, kT, for sustainable rotation around the axis. Under a scanning tunneling microscope, we have imaged live thermal noise movement as a dynamic orbital density and resolved the density diagram up to the second derivative. A second input energy can synchronize multiple rotors to afford a measurable output. Therefore, we hypothesized that rotation control in a DRM must be evolved from an orbital-level information transport channel between the two coupled rotors but was not limited to the second input energy. A DRM comprises a Brownian rotor and a power stroke rotor coupled to a -C≡C- stator, where the transport of information through coupled orbitals between the two rotors is termed the vibrational information flow chain (VIFC). We test this hypothesis by studying the DRM's density functional theory calculation and variable-temperature 1H nuclear magnetic resonance. Additionally, we introduced inbuilt pawl-like functional moieties into a DRM to create different electronic environments by changing proton intercalation interactions, which gated information processing through the VIFC. The results show the VIFC can critically impact the motor's noise harvesting, resulting in variable rotational motions in DRMs.

Quantum Alchemy Based Bonding Trends and Their Link to Hammett's Equation and Pauling's Electronegativity Model.

We present an intuitive and general analytical approximation estimating the energy of covalent single and double bonds between participating atoms in terms of their respective nuclear charges with just three parameters, [EAB ≈ a - bZAZB + c(ZA7/3 + ZB7/3) ]. The functional form of our expression models an alchemical atomic energy decomposition between participating atoms A and B. After calibration, reasonably accurate bond dissociation energy estimates are obtained for hydrogen-saturated diatomics composed of p-block elements coming from the same row 2 ≤ n ≤ 4 in the periodic table. Corresponding changes in bond dissociation energies due to substitution of atom B by C can be obtained via simple formulas. While being of different functional form and origin, our model is as simple and accurate as Pauling's well-known electronegativity model. Analysis indicates that the model's response in covalent bonding to variation in nuclear charge is near-linear, which is consistent with Hammett's equation.

Quantum correlations in molecules: from quantum resourcing to chemical bonding

The second quantum revolution is all about exploiting the quantum nature of atoms and molecules to execute quantum information processing tasks. To boost this growing endeavor and by anticipating the key role of quantum chemistry therein, our work establishes a framework for systematically exploring, quantifying and dissecting correlation effects in molecules. By utilizing the geometric picture of quantum states we compare—on a unified basis and in an operationally meaningful way—total, quantum and classical correlation and entanglement in molecular ground states. To unlock and maximize the quantum informational resourcefulness of molecules an orbital optimization scheme is developed, leading to a paradigm-shifting insight: a single covalent bond equates to the entanglement . This novel and more versatile perspective on electronic structure suggests a generalization of valence bond theory, overcoming deficiencies of modern chemical bonding theories.

A Fruitful Decade of Organofluorine Chemistry: New Reagents and Reactions

A Fruitful Decade of Organofluorine Chemistry: New Reagents and Reactions

Self-correcting energy transfer Diels-Alder adduct dyes

New intramolecular donor-acceptor Diels-Alder adduct dyes were synthesized with different spacer length, which shows high intramolecular energy transfer efficiency. Pure exo and endo isomers of Diels-Alder adduct dyes were isolated and prepared. Single-crystal X-ray diffraction reveals the precise configuration of exo dye isomer, and longer Diels-Alder C–C covalent single bonds than normal single bonds. Time-resolved fluorescence measurements reveal the intramolecular energy transfer process from violet-light emitting donor to green-light emitting acceptor. A rising time of acceptor emission of donor-acceptor dye was observed when the dye donor was excited by nanosecond flash lamp. Low energy transfer dye could be self-corrected into high energy transfer dye by energy donor exchanges.

Toward Density-Based and Simultaneous Description of Chemical Bonding and Noncovalent Interactions with Pauli Energy.

Chemical bonds and noncovalent interactions are extraordinarily important concepts in chemistry and beyond. Using density-based quantities to describe them has a long history in the literature, yet none can satisfactorily describe the entire spectrum of interactions from strong chemical bonds to weak van der Waals forces. In this work, employing Pauli energy as the theoretical foundation, we fill in that knowledge gap. Our results show that the newly established density-based index can describe single and multiple covalent bonds, ionic bonds, metallic bonds, and different kinds of noncovalent interactions, all with unique and readily identifiable signature shapes. Two new descriptors, BNI (bonding and noncovalent interaction) index and USI (ultra-strong interaction) index, have been introduced in this work. Together with NCI (noncovalent interaction) and SCI (strong covalent interaction) indexes already available in the literature, a density-based description of both chemical bonds and noncovalent interactions is accomplished.

Autonomous fuelled directional rotation about a covalent single bond.

Biology operates through autonomous chemically fuelled molecular machinery1, including rotary motors such as adenosine triphosphate synthase2 and the bacterial flagellar motor3. Chemists have long sought to create analogous molecular structures with chemically powered, directionally rotating, components4-17. However, synthetic motor molecules capable of autonomous 360° directional rotation about a single bond have proved elusive, with previous designs lacking either autonomous fuelling7,10,12 or directionality6. Here we show that 1-phenylpyrrole 2,2'-dicarboxylic acid18,19 (1a) is a catalysis-driven20,21 motor that can continuously transduce energy from a chemical fuel9,20-27 to induce repetitive 360° directional rotation of the two aromatic rings around the covalent N-C bond that connects them. On treatment of 1a with a carbodiimide21,25-27, intramolecular anhydride formation between the rings and the anhydride's hydrolysis both occur incessantly. Both reactions are kinetically gated28-30 causing directional bias. Accordingly, catalysis of carbodiimide hydration by the motor molecule continuously drives net directional rotation around the N-C bond. The directionality is determined by the handedness of both an additive that accelerates anhydride hydrolysis and that of the fuel, and is easily reversed additive31. More than 97% of fuel molecules are consumed through the chemical engine cycle24 with a directional bias of up to 71:29 with a chirality-matched fuel and additive. In other words, the motor makes a 'mistake' in direction every three to four turns. The 26-atom motor molecule's simplicity augurs well for its structural optimization and the development of derivatives that can be interfaced with other components for the performance of work and tasks32-36.

Selective hydroboration of terminal alkynes catalyzed by heterometallic clusters with uranium–metal triple bonds

Selective hydroboration of terminal alkynes catalyzed by heterometallic clusters with uranium–metal triple bonds

EDA-NOCV Analysis of Donor-Base-Stabilized Elusive Monomeric Aluminum Phosphides [(L)P-Al(L'); L, L' = cAACMe, NHCMe, PMe3

Herein, we report on the stability and bonding analysis of donor-base-stabilized monomeric AlP species (1–6) of the general formula (L)P–Al(L′); [L = cAACMe, L′ = cAACMe, NHCMe, PMe3, (NiPr2)2 (1–4); L = L′ = NHCMe, PMe3 (5 and 6); cAAC = cyclic alkyl(amino) carbene; NHC = N-heterocyclic carbene]. Energy decomposition analysis coupled with natural orbitals for chemical valence (EDA-NOCV) analysis indicates the synthetic viability of this class of species, stabilized in their singlet ground state, in the laboratory. The CL–P bond is found to be a partial double bond (WBI ∼ 1.45), while the CL/PL–Al bond is a single bond (WBI ∼ 0.42–0.69). These bonds are mostly covalent or dative σ/π bonds depending upon the ligands attached. The central P–Al bond is an electron-sharing covalent polar single bond (WBI ∼ 0.80; P–Al) for 1–4 and a dative σ bond for 5 and 6 (WBI ∼ 0.89–0.93; P–Al). The calculated intrinsic interaction energies of the central P–Al bonds are found to be in the range from −116 to −216 kcal/mol (1–3 and 5 and 6). This value is the highest for compound 3, possibly due to the push and pull effects from the ligands PMe3 and cAAC, respectively.

Partial Double Metal-Carbon Bonding Model in Transition Metal Methyl Compounds.

The chemical bond between a transition metal and a methyl group (M-CH3) is typically defined as a single covalent bond, which is of fundamental significance and general interest in understanding the structural properties and reactivity of transition metal alkyl compounds. Herein, we demonstrate that the M-CH3 bonding involves varying σ and π components and thus should be best described in terms of the partial double M═CH3 bond. The often-neglected π bonding stems from an occupied π-symmetric orbital of the methyl group comprising all three C-H σ bonds (but one C-H' contributes more than the other two) and a vacant low-lying metal d(π) orbital, and is associated with the intramolecular C-H'···M agostic effect (i.e., an acute M-C-H' angle and a short H'···M distance), whose origin is still controversial. We quantify the geometric and energetic impacts of the π interaction involved in the M-CH3 bond by explicitly computing the intramolecular πCH' → dM interaction with the ab initio valence bond (VB) theory. Our computations of the ligand-free [TiCH3]3+ and a series of metallocene catalysts provide a direct proof for the presence of the π bonding in M-CH3 bonds, which is the cause for the agostic effect. The partial double M═CH3 bonding model is not only validated by a range of bonding analyses including VB self-consistent field (VBSCF)-based energy decomposition and quantum theory of atoms in molecules (QTAIM) but also authenticated by the specific activity of double M═CH3 bonds in the C-H activation and olefin insertion. More importantly, the σ bond gradually switches from a classical covalent bond to a novel charge-shift bond with the π bonding becoming increasingly significant. We anticipate that the recognition of the π interaction between electrophilic metal centers and C-H bonds can benefit the understanding of the nature of metal-carbon bonds in transition metal ethyl, alkyl, and carbene compounds.

Stabilisation of Li(0)-Li(0) bond by normal and mesoionic carbenes and electride characteristics of the complexes

Density functional theory (DFT) has been used to study the structure, stability, and bonding in the Li2L2 complexes containing Li(0)-Li(0) bond using both normal and mesoionic carbenes (MICs) as binding ligands (L) with Li2 molecule. The geometries and the nature of bonding of Li2(SNHCMe)2 and Li2(cAACMe)2 normal carbene complexes and Li2(MIC1)2 and Li2(MIC2)2 mesoionic carbene complexes have been compared with the previously reported Li2(NHC)2 normal carbene complex. The stability of the designed complexes is determined by positive Gibbs’ free energy changes (ΔG) towards the dissociation of the complexes into different fragments. Both normal and mesoionic carbenes stabilise the Li2 moiety and both the types of complexes are almost equally stable. From the natural bond orbital (NBO) analysis and the atoms in molecule (AIM) analysis, it is shown that two Li atoms are bonded by a single covalent bond with the oxidation state of zero on each Li. Again, the electron density analysis confirmed that each Li-Li bond has a non-nuclear attractor (NNA) at the middle of the bonds and the values of Laplacian of electron density (∇2 ρ(r)) are negative therein. Both the types of complexes show electride characteristics. The reactivity descriptors of all the studied complexes have been analyzed.

Binary interpnictogen compounds bearing diaryl bismuth fragments bound to all lighter pnictogens.

Multiple interpnictogen compounds with covalent single bonds between a diarylbismuth fragment and all lighter pnictogens were prepared from the corresponding diarylhalido bismuthanes. The aminobismuthanes Ph2BiNMe2 (1) and Mes2BiNMe2 (2) (Mes = 2,4,6-trimethylphenyl-) have been obtained via a salt metathesis reaction and compound 2 was successfully reacted with tBuNH2 in a condensation reaction to yield Mes2BiNHtBu (3). The bismuthanyl phosphanes Ar2BiPtBu2 (Ar = Ph: 4 and Ar = Mes: 5) and arsanes Ar2BiAstBu2 (Ar = Ph: 8 and Ar = Mes: 9) were also obtained via salt metathesis. Through a trimethylsilyl halide abstraction reaction of the diaryl halido bismuthanes and EtBu(SiMe3)2 (E = P and As), the bismuthanyl phosphanes Ar2BiPtBu(SiMe3) (Ar = Ph: 6; Ar = Mes: 7) and the arsanes Ar2BiAstBu(SiMe3) (Ar = Ph: 10; Ar = Mes: 11) have been prepared. Bismuthanyl stibanes were accessed via a condensation reaction of Mes2SbH with 1 or 2, respectively. The compound Ph2BiSbMes2 (12), which has different substituents at the bismuth and antimony atoms, was isolated and fully characterised. In contrast, the isolation of Mes2BiSbMes2 (13) was not possible due to a dynamic equilibrium with Mes4Bi2 and Mes4Sb2 which was investigated via low-temperature 1H-NMR spectroscopy in solution. The isolated compounds with a single bond between bismuth and the heavy pnictogens arsenic and antimony are rare examples of their kind. All isolated compounds (1-12) were characterised by NMR and IR spectroscopy, mass spectrometry, elemental analysis and single crystal X-ray diffraction.

A Dual-Responsive Peptide-Based Smart Biointerface with Biomimetic Adhesive Behaviors for Bacterial Isolation.

As mimics of the extracellular matrix, surfaces with the capability of capturing and releasing specific cells in a smart and controllable way play an important role in bacterial isolation. In this work, we fabricated a dual-responsive smart biointerface via peptide self-assembly and reversible covalent chemistry biomimetic adhesion behavior for bacterial isolation. Compared with that of the biointerface based on a single reversible covalent bond, the bacterial enrichment efficiency obtained in this work was 2.3 times higher. Furthermore, the release of bacteria from the surface could be achieved by dual responsiveness (sugar and enzyme), which makes the biointerface more adaptable and compatible under different conditions. Finally, the reusability of the biointerface was verified via peptide self-assembly and the regenerated smart biointerface still showed good bacterial capture stability and excellent release efficiency, which was highly anticipated to be more widely applied in biomaterial science and biomedicine in the future.