Inversion Barrier Research Articles

Benzo-Fused Phosphepines: Synthesis by Gold(I)-Catalyzed Intramolecular Hydroarylation and Ring Inversion.

Gold(I)-catalyzed intramolecular hydroarylation of dialkynyl(biaryl)phosphine oxides provided versatile benzo-fused phosphepine oxides. O-exo adducts were obtained as the major product, and O-endo adducts were the minor product. O-exo and O-endo indicate the position of an oxygen atom with respect to the central phosphepine framework. The isomers of dibenzo[b,d]phosphepine oxides with methyl and phenyl groups in an adjacent position (shown as 2a and 3a in the main text) were determined by X-ray crystallographic analysis. O-exo and O-endo adducts are diastereomers owing to the central chirality of the phosphorus atom and the planar chirality of phosphepine, and they are interconverted through a ring inversion of phosphepine via a transition state with a planar structure. The inversion barrier, fully estimated through theoretical calculations, drasticallyvaried depending on the substituents in the phosphepine framework and/or the fusion of benzene and thiophene rings. Furthermore, the kinetics of the thermal isomerization of less stable O-endo product 3a into O-exo product 2a was examined.

Unraveling the Stereoisomer Configurations of 1,1'-bis(tert-butylphosphino)Ferrocene in the Gas Phase.

The molecular structure of a ferrocene derivative with adjacent centers of chirality, 1,1'-bis(tert-butylphosphino)ferrocene, has been examined in the gas phase using broadband microwave spectroscopy under the isolated and cold conditions of a supersonic jet. The diastereomers of 1,1'-bis(tert-butylphosphino)ferrocene can adopt homo- and hetero-chiral configurations, owing to the P-chiral substituents on the cyclopentadienyl rings. Moreover, the internal ring rotation of each diastereomer gives rise to four conformers with eclipsed ring arrangements, where the two tert-butylphosphino groups were separated by dihedral angles of approximately 72°, 144°, 216°, and 288° with respect to the two ring centers. The interconversion barriers between the conformations are below 2 kJ/mol, whereas the pyramidal inversion of the tert-butylphosphino groups is hindered by more than 140 kJ/mol, calculated at the B3LYP-D3(BJ)/def2-QZVP level of theory. In the experimental microwave spectrum, we unambiguously identified the two global-minimum diastereomers with 72° conformations. The absence of other conformers can be attributed to the relaxation dynamics in the supersonic jet, which transfers the high-energy conformers to the respective global-minimum geometries. Additionally, we discovered that London dispersion interactions between the two tert-butylphosphino groups play a crucial role in stabilizing the structures of this ferrocene complex.

Exploring Benzothieno[3,2-b]benzothiophene S-Oxides for Organic Electronics, Fluorescence-Based Applications, and Asymmetric Synthesis.

A series of benzothieno[3,2-b]benzothiopheneS-oxides has been efficiently synthesized via one- or two-step selective oxidation of benzothieno[3,2-b]benzothiophene (BTBT). These BTBTS-oxides form highly ordered structures that display optical anisotropy, are thermally stable up to temperatures above 210 oC, and do not show phase transitions. They exhibit long excited state lifetimes (0.181-0.869 ms) and are more resistant to oxidative degradation than their parent unoxidized BTBT. Some of these compounds demonstrate high quantum yields, exceeding 98% in solution and 71% in the solid state. As evidenced by quantum-chemical calculations, BTBT-based sulfoxides have sufficiently high pyramidal inversion energy barriers that prevent their stereomutation at room temperature. Additionally, fully S-oxidized BTBT meets the energy-splitting criterion required for the singlet fission process, with the T1 energy level that makes it suitable for device application.

Asymmetric S-Arylation of Sulfenamides to Access Axially Chiral Sulfilimines Enabled by Anionic Stereogenic-at-Cobalt(III) Complexes.

An efficient enantioselective coupling reaction between sulfenamides and cyclic diaryliodonium salts is established via adaptive Cu/anionic stereogenic-at-Co(III) complex combined catalysis, precisely synthesizing a broad range of axially chiral sulfilimines with excellent enantioselectivities, diastereoselectivities, regioselectivities, and chemoselectivities (67 examples under same conditions, up to 98 % ee). The following thermodynamically controlled pyramidal inversion enables efficient stereodivegent synthesis of all four stereoisomers. Mechanistic studies suggest that anionic stereogenic-at-cobalt(III) complexes serve as counteranions of diaryliodonium and anionic ligand of Cu(I) catalyst simultaneously, which could be regarded as an explanation for outstanding selectivities.

Asymmetric S‐Arylation of Sulfenamides to Access Axially Chiral Sulfilimines Enabled by Anionic Stereogenic‐at‐Cobalt(III) Complexes

AbstractAn efficient enantioselective coupling reaction between sulfenamides and cyclic diaryliodonium salts is established via adaptive Cu/anionic stereogenic‐at‐Co(III) complex combined catalysis, precisely synthesizing a broad range of axially chiral sulfilimines with excellent enantioselectivities, diastereoselectivities, regioselectivities, and chemoselectivities (67 examples under same conditions, up to 98 % ee). The following thermodynamically controlled pyramidal inversion enables efficient stereodivegent synthesis of all four stereoisomers. Mechanistic studies suggest that anionic stereogenic‐at‐cobalt(III) complexes serve as counteranions of diaryliodonium and anionic ligand of Cu(I) catalyst simultaneously, which could be regarded as an explanation for outstanding selectivities.

Suppressing Inversion of a Chiral Polycyclic Aromatic Aza Monkey Saddle by Molecular Editing

AbstractChiral polycyclic aromatic hydrocarbons with monkey saddle topology are a fascinating class of negatively curved compounds. To make the monkey‐saddles valuable building blocks for chirality‐assisted synthesis (CAS) approaches, the inversion barriers between the two possible enantiomers need to be high enough to prevent interconversion under CAS conditions. By molecular editing, aza monkey saddles were converted to the corresponding chromene monkey saddles that are configurationally stable even at temperatures of 220 °C over a period of 47 days. Their structures were studied by single X‐ray diffraction and enantiomers were separated to study the chiroptical properties. Furthermore, mechanistic assumptions of the formation of the chromene monkey saddles by DFT calculations are discussed.

A Theoretical Study of Positively Curved Circulenes Embedded with Five-Membered Heterocycles: Structures and Inversions.

Recently, polycyclic arenes with positive curvature have gained increasing significance in the field of material chemistry. This study specifically explores the inversion barriers of a series of positively curved circulenes by using five-membered heterocycles integrated into the backbone of primitive [5]circulenes and [6]circulenes. For hetero[5]circulenes, where one benzenoid ring is replaced by a heterocycle, the inversion barriers exhibit a strong correlation with the rotary angles of the heterocycles, and larger rotary angles result in lower inversion barriers. Additionally, the aromaticity of the circulene undergoes a significant reduction during the inversion process. As the number n of replaced rings increases, the inversion barriers can be adjusted, demonstrating an almost linear relationship with n. In the case of hetero[6]circulenes, molecules bearing heterocycles with small rotary angles also show positive curvatures. Furthermore, we examine the relationship between the radii of the fitted sphere for the circulenes and the inversion barriers, revealing an intriguing inverse proportionality between the fourth power of the radius and the inversion barrier. We anticipate that this research will offer a fresh perspective on studies related to positively curved polycyclic arenes.

Exciting Novel Polyaspartates: Design, Synthesis, and Photo-Responsive Behavior in Solution and Lyotropic Liquid Crystalline Phase Upon Irradiation with Visible Light.

Many polypeptides form stable, helical secondary structures enabling the formation of lyotropic liquid crystalline (LLC) phases. Contrary to the well-studied polyglutamate, their counterparts based on polyaspartates exhibit a much lower helix inversion barrier. Therefore, the helix sense is not solely dictated by the chirality of the amino acid used, but additionally by the nature and conformation of the polymer sidechain. In this work, polymers responsive to irradiation with visible light are designed achieving conformational transitions from helix-to-coil and helix-to-helix. The synthesis and the application as LLC mesogens of several (co-)polyaspartates bearing ortho-fluorinated azobenzene (FAB) as a photochromic group are presented. Many of the obtained polymers undergo changes in their secondary structure upon E-Z-isomerization of the FAB-containing sidechain. Of special interest are copolymers that exhibit photo-responsive helix inversion without loss of their helical secondary structure. These copolymers form stable LLC phases in helicogenic solvents, where the effect of photo-switching on the macroscopic behavior is studied by NMR spectroscopy. Especially, the irradiation of the different LLC phases of the helix inversion polymers displays a change in the LLC order experienced by the solvent. These peculiar properties are promising for future applications as photo-responsive alignment media for structure elucidation in NMR.

Migration of para-Nitrophenyl Groups in Methyl Pyranosides: Configuration and Conformation Determine the Kinetics.

para-Nitrophenyl (PNP) ethers of glycosides are important building blocks en route to functional carbohydrates. They are stable in neutral media, however, under basic conditions such as during the Zemplén deacylation of sugars, aryl migration is frequently observed. We have employed a library of O-PNP-substituted methyl glycosides of the manno-, galacto-, gluco- and altro-series to study the kinetics of aryl migration in MeOH/sodium methoxide using NMR spectroscopy revealing that migration between cis-oriented OH groups is faster than between trans-oriented ones. The rate constants of migration decrease in the order of Alt>Man>Gal>Glc and are related to the energy barriers of chair conformation inversion. The energy profile of the 3 to 4-PNP migration in methyl mannoside was calculated using DFT methods suggesting the Meisenheimer complex is an intermediate of PNP migration and that coordination of the sodium cation has a major impact on the energy profile.

Acene-Integrated Buckybowls with Near-Infrared II Absorption and over 90 % Photothermal Conversion Efficiency.

Tetracene and pentacene are large, promising building blocks for construction of complex molecular nanocarbons due to their extraordinary photophysical and electronic properties. Herein, two acene-integrated buckybowls, composed of two rows of tetracenes and pentacenes fused through s-indacene unit at the zigzag edges, have been synthesized and characterized. Compared to parent tetracene and pentacene, the buckybowls are extremely stable and show much smaller electrochemical band gaps. Kinetic studies gave the bowl-to-bowl inversion barriers of 11.7 and 13.3 kcal mol-1. Subsequent investigations on magnetic ring currents revealed two local diatropic currents at two rows of acenes and one paratropic current at the s-indacene unit, respectively. Notably, both buckybowls show a broad absorption that reaches into near-infrared II region, and a high photothermal conversion efficiency (>90 %) was achieved when exposed to near-infrared 1064 nm laser photo-irradiation. This study highlights the unusual nature of merging the intrinsic properties of acenes with the inherent properties of buckybowls and showcases a potential avenue for acene utilization for the design of novel complex nanocarbons with a broad range of applications.

Acene‐Integrated Buckybowls with Near‐Infrared II Absorption and over 90 % Photothermal Conversion Efficiency

AbstractTetracene and pentacene are large, promising building blocks for construction of complex molecular nanocarbons due to their extraordinary photophysical and electronic properties. Herein, two acene‐integrated buckybowls, composed of two rows of tetracenes and pentacenes fused through s‐indacene unit at the zigzag edges, have been synthesized and characterized. Compared to parent tetracene and pentacene, the buckybowls are extremely stable and show much smaller electrochemical band gaps. Kinetic studies gave the bowl‐to‐bowl inversion barriers of 11.7 and 13.3 kcal mol−1. Subsequent investigations on magnetic ring currents revealed two local diatropic currents at two rows of acenes and one paratropic current at the s‐indacene unit, respectively. Notably, both buckybowls show a broad absorption that reaches into near‐infrared II region, and a high photothermal conversion efficiency (>90 %) was achieved when exposed to near‐infrared 1064 nm laser photo‐irradiation. This study highlights the unusual nature of merging the intrinsic properties of acenes with the inherent properties of buckybowls and showcases a potential avenue for acene utilization for the design of novel complex nanocarbons with a broad range of applications.

Twist along Central C-C Bonds in a Series of Fully π-Fused Propellanes.

Without stereogenic carbon centers, organic molecules can be chiral when they have large energy barriers for conformational inversion. In this work, conformational behaviors are investigated for a series of tricyclic propellane skeletons with increasing 6-membered-ring peripheral moieties fused with aromatic rings. According to theoretical calculations, trinaphtho[3.3.3]propellane has three vertical naphthalene rings like triptycene shape without torsion along the central C-C single bond. On the other hand, hexabenzo[4.4.4]propellane shows hexaphenylethane-like ca. 60° twist along the bond with large activation energy of 64 kcal mol-1 for twist inversion because of the high congestion caused by three 6-membered-ring loops. Indeed, the [4.4.4]propellane gives a stable pair of chiroptical enantiomers toward heating at 146 °C. By contrast, a hybrid [4.3.3]propellane exhibits fast interconversion between two twisted conformations even at -80 °C.

Chiral Teropyrenes: Synthesis, Structure, and Spectroscopic Studies

AbstractWe present the inaugural synthesis of a chiral teropyrene achieved through a four‐fold alkyne benzannulation catalyzed by InCl3, resulting in good yields. The product underwent thorough characterization using FT‐Raman and FT‐IR spectroscopies, demonstrating a close agreement with calculated spectra. X‐ray crystallographic analysis unveiled a notable twist in the molecule‘s backbone, with an end‐to‐end twist angle of 51°, consistent with computational predictions. Experimentally determined enantiomeric inversion barriers revealed a significant energy barrier of 23 kcal/mol, facilitating the isolation of enantiomers for analysis by circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopies. These findings mark significant strides in the synthesis and characterization of chiral teropyrenes, offering insights into their structural and spectroscopic properties.

Chiral Teropyrenes: Synthesis, Structure, and Spectroscopic Studies.

We present the inaugural synthesis of a chiral teropyrene achieved through a four-fold alkyne benzannulation catalyzed by InCl3, resulting in good yields. The product underwent thorough characterization using FT-Raman and FT-IR spectroscopies, demonstrating a close agreement with calculated spectra. X-ray crystallographic analysis unveiled a notable twist in the molecule's backbone, with an end-to-end twist angle of 51°, consistent with computational predictions. Experimentally determined enantiomeric inversion barriers revealed a significant energy barrier of 23 kcal/mol, facilitating the isolation of enantiomers for analysis by circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopies. These findings mark significant strides in the synthesis and characterization of chiral teropyrenes, offering insights into their structural and spectroscopic properties.

Synthesis and Conformational Dynamics of Selenanthrene (Oxides): Establishing an Energetic Flexibility Index for Scaffolds.

The use of new dynamic scaffolds for constructing inorganic and organometallic complexes with enhanced reactivities is an important new research direction. Toward this fundamental aim, an improved synthesis of the dynamic scaffold selenanthrene, along with its monoxide, trans-dioxide and the previously unknown trioxide, is reported. A discussion of the potential reaction mechanism for selenanthrene is provided, and all products were characterized using 1H, 13C, and 77Se nuclear magnetic resonance (NMR) spectroscopy and single-crystal X-ray crystallography. The dynamic ring inversion processes (i.e., "butterfly motion") for selenanthrene and its oxides were investigated using variable-temperature 1H NMR and density functional theory calculations. The findings suggest that selenanthrene possesses a roughly equal barrier to inversion as its sulfur analogue, thianthrene. However, selenanthrene oxides evidently possess larger inversion barriers as compared to their sulfur analogues due to the enhanced electrostatic intramolecular interactions inherent between the highly polar selenium-oxygen bond and adjacent C-H moieties. Finally, we propose a quantitative "flexibility index" in deg/(kcal/mol) for various tricyclic scaffolds to provide researchers with a comparative scale of dynamic motion across many different systems.

Generation of out-of-plane ferroelectric behavior in a one-atom-thick monolayer

Ferroelectricity with out-of-plane polarization has so far been found in several two-dimensional (2D) materials, including monolayers comprising three to five planes of atoms, e.g. α-In2Se3 and MoTe2. Here, we explore the generation of out-of-plane polarization within a one-atom-thick monolayer material, namely hexagonal boron nitride. We performed density-functional-theory calculations to explore inducing ferroelectric-like distortions through incorporation of isovalent substitutional impurities that are larger than the host atoms. This disparity in bond lengths causes a buckling of the h-BN, either up or down, which amounts to a dipole with two equivalent energies and opposing orientations. We tested several impurities to explore the magnitude of the induced dipole and the switching energy barrier for dipole inversion. The effects of strain, dipole–dipole interactions, and vertical heterostructures with graphene are further explored. Our results suggest a highly-tunable system with ground state antiferroelectricity and metastable ferroelectricity. We expect that this work will help foster new ways to include functionality in layered 2D-material-based applications.

Palladium-catalyzed asymmetric carbene coupling en route to inherently chiral heptagon-containing polyarenes.

Developing facile and direct synthesis routes for enantioselective construction of cyclic π-conjugated molecules is crucial. However, originate chirality from the distorted structure around heptagon-containing polyarenes is largely overlooked, the enantioselective construction of all-carbon heptagon-containing polyarenes remains a challenge. Herein, we present a highly enantioselective synthesis route for fabricating all carbon heptagon-containing polyarenes via palladium-catalyzed carbene-based cross-coupling of benzyl bromides and N-arylsulfonylhydrazones. A wide range of nonplanar, saddle-shaped tribenzocycloheptene derivatives are efficiently prepared in high yields with excellent enantioselectivities using this approach. In addition, stereochemical stability experiments show that these saddle-shaped tribenzocycloheptene derivatives have high inversion barriers.

Ligand Centered Reactivity of a Transition Metal Bound Geometrically Constrained Phosphine.

The electronic properties, coordination chemistry and reactivity of metal complexes of a planar (C2v symmetric) acridane-derived geometrically constrained phosphine, P(NNN), are described. On complexation to metal centers, the phosphine was found to adopt a distorted trigonal pyramidal structure with a high barrier to pyramidal inversion (22.3 kcal/mol at 298 K for Au[P(NNN)]Cl). Spectroscopic data and theoretical calculations carried out at the density functional level of theory indicate that P(NNN) is a moderate σ-donor, with significant π-acceptor properties. Despite the distortion undergone by the phosphorus atom on coordination to metal centers, the P(NNN) ligand retains its ability to react with small molecule substrates with polar E-H bonds (MeOH, NH2Ph, NH3). It does so in a concerted fashion across one of the P-N bonds, and reversibly in the case of amine substrates. This cooperative bond activation chemistry may ultimately prove beneficial in catalysis.

Three DOF Rotation Compensation in Floating HFSWR for Ocean Current Inversion

High-frequency surface wave radar (HFSWR) has been widely used for ocean surface current inversion. Floating this radar can realize the ocean surface inversion among large areas far away from the coastline. However, six degree-of-freedom (DOF) movements will set the barrier for the ocean current inversion on its radial velocity estimation and direction of arrival estimation. Among these movements, three DOF rotations can cause both Doppler modulation and azimuth modulation while three DOF translations only cause Doppler modulation which is dependent on the arrival direction of echoes. Hence, the analysis and compensation for three DOF rotations are first to be solved. In this paper, we analyse the Doppler modulation and azimuth modulation of three DOF rotations and further develop the global adaptive beamforming method to compensate for these rotations. Adaptive beamforming is used to compensate for rotations to make the real-time beams fixed to the ground when the platform is rotating. Simulations indicate that the global adaptive beamforming can perfectly compensate for the reasonable rotations, among which the yaw rotation is the dominant factor for both Doppler spectrum modulation and azimuth modulation. The rotation compensation using global adaptive beamforming can greatly improve the precision of ocean surface inversion.

Pyramidal inversion in the solid state

For the first time, the stereochemical phenomenon of pyramid inversion was observed in the solid state, solely driven by applying external pressure.