Exploring London Dispersion and Solvent Interactions at Alkyl–Alkyl Interfaces Using Azobenzene Switches

Interactions on the molecular level control structure as well as function. Especially interfaces between innocent alkyl groups are hardly studied although they are of great importance in larger systems. Herein, London dispersion in conjunction with solvent interactions between linear alkyl chains was examined with an azobenzene‐based experimental setup. Alkyl chains in all meta positions of the azobenzene core were systematically elongated, and the change in rate for the thermally induced Z→E isomerization in n‐decane was determined. The stability of the Z‐isomer increased with longer chains and reached a maximum for n‐butyl groups. Further elongation led to faster isomerization. The origin of the intramolecular interactions was elaborated by various techniques, including ¹H NOESY NMR spectroscopy. The results indicate that there are additional long‐range interactions between n‐alkyl chains with the opposite phenyl core in the Z‐state. These interactions are most likely dominated by attractive London dispersion. This work provides rare insight into the stabilizing contributions of highly flexible groups in an intra‐ as well as an intermolecular setting.     

Attraction or Repulsion? London Dispersion Forces Control Azobenzene Switches

Large substituents are commonly seen as entirely repulsive through steric hindrance. Such groups have additional attractive effects arising from weak London dispersion forces between the neutral atoms. Steric interactions are recognized to have a strong influence on isomerization processes, such as in azobenzene‐based molecular switches. Textbooks indicate that steric hindrance destabilizes the Z isomers. Herein, we demonstrate that increasing the bulkiness of electronically equal substituents in the meta‐position decreases the thermal reaction rates from the Z to the E isomers. DFT computations revealed that attractive dispersion forces essentially lower the energy of the Z isomers.     

A Sandwich Azobenzene–Diamide Dimer for Photoregulated Chloride Transport

There has been a tremendous evolution for artificial ion transport systems, especially gated synthetic systems, which closely mimic their natural congeners. Herein, we demonstrate a trans-azobenzene-based photoregulatory anionophoric system that transports chloride by forming a sandwich dimeric complex. Further studies confirmed a carrier-mediated chloride-anion antiport mechanism, and the supramolecular interactions involved in chloride recognition within the sandwich complex were revealed from theoretical studies. Reversible trans–cis photoisomerization of the azobenzene was achieved without any significant contribution from the thermal cis→trans isomerization at room temperature. Photoregulatory transport activity across the lipid bilayer membrane inferred an outstanding off-on response of the azobenzene photoswitch.     

QM/MM Studies on Photoisomerization Dynamics of Azobenzene Chromophore Tethered to a DNA Duplex: Local Unpaired Nucleobase Plays a Crucial Role

The photoresponsive azobenzene‐tethered DNAs have received growing experimental attention because of their potential applications in biotechnology and nanotechnology; however, little is known about the initial photoisomerization of azobenzene in these systems. Herein we have employed quantum mechanics/molecular mechanics (QM/MM) methods to explore the photoisomerization dynamics of an azobenzene‐tethered DNA duplex. We find that in the S₁ state the trans–cis photoisomerization path is much steeper in DNA than in vacuo, which makes the photoisomerization much faster in the DNA environment. This acceleration is primarily caused by complex steric interactions between azobenzene and the nearby unpaired thymine nucleobase, which also change the photoisomerization mechanism of azobenzene in the DNA duplex.     

Impact of silica nanoparticles dispersion on the dielectric and electro-optical properties and absorption spectra of host ferroelectric liquid crystal

The present work concerns with the investigation of the effect of dispersion of Silica (SiO₂) nanoparticles (NPs) in host ferroelectric liquid crystal (FLC) KCFLC10S on the dielectric and electro-optical properties and ultraviolet-visible (UV-VIS) absorption spectra of the pristine and dispersed systems. We have found that the dispersion of SiO₂ NPs in the host FLC strongly influences the various properties of dispersed systems. No evidence of aggregates and clumps in the dispersed system has been observed. Due to SiO₂ NPs dispersion, a rapid decrease in dielectric permittivity ε’, increase in conductivity σ with frequency, increase in spontaneous polarisation P_s and decrease in switching time with bias voltage have been observed. Based on the absorption spectra, we have also made an attempt to link the electro-optical and dielectric response with the mechanism of FLC–NPs interactions.     

Acid–base complexes of polymers

The physical interactions of polymers with neighboring molecules are determined by only two kinds of interactions: London dispersion forces and Lewis acid–base interactions. These two kinds of attractive energies (together with certain steric restrictions) determine solubility, solvent retention, plasticizer action, wettability, adsorption, adhesion, reinforcement, crystallinity, and mechanical properties. The London dispersion force interaction energies of polymers have been quantified by the dispersion force contribution to cohesive energy density (δ²_d) and the dispersion force contribution to surface energy (δ^d). The Lewis acid–base interactions, often referred to as “polar” interactions, can be best quantified by Drago's C_A and E_A constants for acid sites and C_B and E_B constants for basic sites. In this article infrared spectral shifts are featured as a method of determining enthalpies of acid–base interaction, and the C and E constants for polymers, plasticizers, and solvents. Examples are given where acid–base complexation of polymers with solvents dominate solubility and swelling phenomena. Enthalpies of acid–base complexation in polymer blends are determined from spectral shifts.     

Fluorine‐substituted azobenzene destabilizes polar form of optically switchable fulgimide unit in copolymer system

Fulgimide and various size and electronic nature of substituents on the terminal position of azobenzene in the pendant homo/copolymethacrylates were synthesized. Differential scanning calorimetry analysis indicates the homopolymer possessing C‐form fulgimide unit exhibited higher T_m than that of E‐form of the homopolymer and revealed C‐form is highly ordered. Thermal stability suggests azobenzene homopolymers with electron donating substituents have high thermal stability than electron withdrawing substituents. Polarized optical microscopy observation disclosed homopolymers viz., NI, CY, FL, ME , and T‐ME exhibited liquid crystalline mesophases between their T_m and T_i. Optical properties of homo/copolymers were investigated by UV–vis and fluorescence spectroscopy. UV–vis spectroscopy displayed C‐form fulgimide absorption in F‐co‐FL around 482 nm which is around 40 nm lesser than C‐form of substituted azobenzene copolymers. Similarly, fluorescence pattern of F‐co‐FL by UV irradiation exhibited emission intensity slowly increased to certain level then decreases with two new emissions at 430 and 480 nm attributed to terminal position of fluorine atom on azobenzene destabilizes polar form (C‐form) fulgimide unit in the copolymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1565–1578, 2010     

Enhanced Aerogen–π Interaction by a Cation–π Force

The interaction between a noble gas atom and an aromatic π‐electron system, which mainly originates from the London dispersion force, is very weak and has not attracted enough attention yet. Herein, we reported a type of notably enhanced aerogen–π interaction between cation–π systems and noble gas atoms. The binding strength of a divalent cation–π system with a xenon atom is comparable to a moderate hydrogen bond (up to ca. 7 kcal mol^?1), whereas krypton and argon atoms produce slightly weaker interactions. Energy‐decomposition analysis reveals that the induction interaction is responsible for the stabilization of divalent cation–π?Xe species besides the dispersion interaction. Our results might be helpful to increase the understanding of some unsolved mysteries of aerogens.     

London Dispersion and Hydrogen-Bonding Interactions in Bulky Molecules: The Case of Diadamantyl Ether Complexes

Diadamantyl ether (DAE, C₂₀H₃₀O) represents a good model to study the interplay between London dispersion and hydrogen-bond interactions. By using broadband rotational spectroscopy, an accurate experimental structure of the diadamantyl ether monomer is obtained and its aggregates with water and a variety of aliphatic alcohols of increasing size are analyzed. In the monomer, C−H⋅⋅⋅H−C London dispersion attractions between the two adamantyl subunits further stabilize its structure. Water and the alcohol partners bind to diadamantyl ether through hydrogen bonding and non-covalent O_{water/alcohol}⋅⋅⋅H−C_DAE and C−H_alcohol⋅⋅⋅H−C_DAE interactions. Electrostatic contributions drive the stabilization of all the complexes, whereas London dispersion interactions become more pronounced with increasing size of the alcohol. Complexes with dominant dispersion contributions are significantly higher in energy and were not observed in the experiment. The results presented herein shed light on the first steps of microsolvation and aggregation of molecular complexes with London dispersion energy donor (DED) groups and the kind of interactions that control them.     

Synthesis of methyl‐substituted azobenzene–carbazole conjugated copolymers with photoinduced structural changes

Azobenzene switches its structure instantaneously by reversible trans‐to‐cis and cis‐to‐trans photoisomerization with light irradiations. Dynamic change in polymer structure is expected via introducing an azobenzene unit into the main chain. In this study, a set of methyl‐substituted azobenzene–carbazole conjugated copolymers is synthesized by the Suzuki–Miyaura coupling method. Introduction of methyl substituents to the azobenzene unit of the monomer, and polymerization in a high‐boiling solvent improve the molecular weight of the polymer. Decrease of effective conjugation length due to the twisted structure of the main chain allows progress of photoisomerization. The microstructure of the polymer was determined with grazing incidence X‐ray diffraction (GIXD) measurements using synchrotron radiation. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1756–1764     

Through-Space Polar-π Interactions in 2,6-Diarylthiophenols

Molecular recognition between polar groups and aromatic molecules is fundamentally important to rational drug design. Although it has been well established that many polar functionalities interact with electron-rich aromatic residues through energetically favorable polar-π interactions, there is a limited understanding of the association between thiols and aromatic systems. Herein we report physical-organic chemistry studies on 2,6-diarylthiophenols that possess the central thiophenol ring and two flanking aromatic rings with tunable electronic properties caused by substituents at distant para position. Hammett analysis revealed that pK_a values and proton affinities correlate well with Hammett sigma values of substituents. Additional energy decomposition analysis supported the conclusion that both through-space SH-π interactions and S⁻-π interactions contribute to intramolecular stabilization of 2,6-diarylthiophenols.     

Synthesis and mesomorphic properties and optical behaviour analysis of homologous series azobenzene liquid crystal monomer with polar substituents

ABSTRACT

Twenty novel azobenzene liquid crystal micromolecular compounds named ω-[4-(p-substituted azobenzeneoxy carbonyl]acid (X-ABCnA) have been designed and synthesised, followed by studies on the thermal performance and mesomorphic properties of the compounds. The liquid crystal compounds were divided into five homologous series based on the terminal substituents R (R = CH₃O, CH₃, H, Cl, NO₂). In each series, the number of carbons on flexible chain was 4, 6, 8 and 10, respectively. Fourier-transform infrared, proton nuclear magnetic resonance and elementary analysis demonstrated that the structure of the synthesised azobenzene liquid crystal compounds was consistent with the molecular design. The mesomorphic properties were tested, analysed and characterised by using differential scanning calorimetry and polarised optical microscopy. The melting transition (T _m) of all the compounds in homologous series with different substituents appeared to decrease with the increase of carbon numbers on flexible chains. The same held true for the temperature of isotropic-mesophase/crystalline transition. The compounds with stronger polarity of terminal substituents were more likely to form broader mesogenic ranges. The liquid crystal compounds discussed in this work can be regarded as a reference for the synthesis of mesogenic arms participating in the synthesis of novel multi-arm liquid crystalline macromolecules and polymers.     

Photooptical Properties of Polymethacrylates Having Cyanoazobenzene‐Containing Side Groups with Lateral Methyl Substituents and Different Spacer Length

New photochromic polymethacrylates with different spacer length having azobenzene side groups and lateral methyl substituents were synthesized. The phase behavior of polymethacrylates and their photooptical properties were studied and compared with unsubstituted analogues. It is shown that an introduction of lateral methyl substituents results in almost complete suppression of liquid crystalline (LC) phase formation and strong decrease of photoinduced dichroism values. It is found that rates of the photoinduced E‐Z isomerization and back thermal Z‐E isomerization are almost independent on spacer lengths. Due to the presence of lateral substituents, the photoinduced azobenzene Z‐form shows remarkable long lifetime, and back thermal conversion at room temperature takes more than 10 days. Specific peculiarities of the photoorientation process in polymer films under the polarized UV and visible light action were studied and their mechanism is suggested. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1337–1342     

Gas-Chromatographic Study of the Polarity and Selectivity of Nematic Liquid Crystals

The sorption properties of stationary phases based on nematic p-substituted azoxybenzenes were studied. Correlations were revealed between the structural selectivity of mesogens, chemical nature of terminal substituents, capability for dispersion interactions and polarity of the sorbents, temperature gradient of the retention indices, and thermodynamic parameters of solution of xylene isomers in the sorbents.     

Azobenzene‐containing LC polymethacrylates highly photosensitive in broad spectral range

Two photosensitive chiral liquid crystalline azobenzene‐containing polymethacrylates having different length of flexible spacer connecting chromophores with backbone were synthesized and their phase behavior and photo‐optical properties were studied. Both polymers consist of lateral methyl substituents in ortho‐position of azobenzene chromophores providing high photosensitivity even in red spectral region as well as high thermal stability of photoinduced Z‐form of azobenzene chromophores. It is shown, that smectic phase (SmA*) formation in films of polymer with longer spacer predetermines its quite unusual spectral response to UV and subsequent visible light actions. The SmA* phase promotes spontaneous homeotropic alignment of azobenzene chromophores in polymer films. UV‐irradiation induces not only E‐Z isomerization but also results in disruption of homeotropic alignment, whereas subsequent visible light action enables to obtain films with the low degree of chromophores orientation. The photo‐orientation phenomena under the action of polarized light of different wavelength on polymer films were studied. The possibility of using red polarized light of moderate intensity for optical photorecording on polymer films is demonstrated. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2962–2970     

Attractive Dispersion Interactions Versus Steric Repulsion of tert‐Butyl groups in the Crystal Packing of a D3h‐Symmetric Tris(quinoxalinophenanthrophenazine)

The crystalline packing of a π‐extended D_3h‐symmetric triptycene reveals a particular π stacking motif with an almost‐eclipsed arrangement of adjacent π planes despite the steric repulsion of tert‐butyl substituents. Four model compounds were analyzed by using single‐crystal X‐ray diffraction and theoretical calculations to study the influence of dispersion interactions of molecular parts and understand the relationship between the molecular structure and this unique packing motif.     

Substituent effects on noncovalent halogen/π interactions: Theoretical study

Noncovalent halogen/π interactions of FCl with substituted benzenes have been investigated using ab initio calculations. It was shown that the predicted maximum interaction energy gap between the substituted and unsubstituted systems amounts to 1.14 kcal/mol, and therefore substituents on benzene have a pronounced effect on the strength of halogen/π interactions. While the presence of electron‐donating groups (NH₂, CH₃, and OH) on benzene enhances the interaction energy appreciably, an opposite effect is observed for electron‐accepting groups (NO₂, CN, Br, Cl, and F). The large gain of the attraction by electron correlation illustrates that the stabilities of the systems considered arise primarily from the dispersion interaction. Beside the dispersion interaction, the charge‐transfer interaction also plays an important role in halogen/π interactions, as a charge density analysis suggested. To provide more insight into the nature of halogen/π interactions, topological analysis of the electron density distribution and properties of bond critical points were determined in terms of the atoms in molecules (AIM) theory. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

On the nature of the interaction between H2 and metal-organic frameworks

The mechanism of adsorption of molecular hydrogen (H₂) on IRMOF-1 is studied at the MP2 level. The role of the two principal MOF components, the inorganic connector and the organic linker, for H₂ adsorption is evaluated. Correlation methods and large basis sets are necessary to describe correctly the weak interactions (London dispersion) and to account for the polarisability of H₂. We proof that the electrostatic interactions have a negligible contribution to the interaction energy and the adsorption mechanism is governed by London dispersion (3–5 kJ mol^?1).     

Optical behaviour of photoimageable cholesteric liquid crystal cells with various novel chiral compounds

In theory, both polarity and steric hindrance are basic factors which affect molecular interactions. To investigate the optical properties and steric structures of chiral compounds having different chiral moieties which affect the wavelength of light reflection in liquid crystal (LC) cells, a series of novel chiral compounds and azobenzene derivatives were synthesized. The liquid crystalline phases of the compounds were identified using small angle X‐ray diffraction, differential scanning calorimetry and polarizing optical microscopy. Cholesteric LC cells with various synthesized chiral dopants which selectively reflect visible light were first prepared, the photochemical switching behaviour of colours was then investigated, with special reference to the change in transmittance in cholesteric LC cells containing an azobenzene derivative as a photoisomerizable guest molecule. Reversible isomerization of azobenzene molecules occurred in the cholesteric systems, resulting in a depression of T _ChI and a shift of the selectively reflected wavelength. We discuss the photochemically driven change in the helical pitch of the cholesteric LCs with respect to structural effects involving the chiral moieties. Molecular interactions caused by the added dopants, reliability and stability of the photoisomerization, and UV irradiation effects on the cholesteric LC cells were also investigated. A real image was recorded through a mask on a cholesteric LC cell fabricated in this investigation.