Search Results (8)

In this work, we have observed that some chiral boron clusters (${\mathrm{B}}_{16}^{-}$, ${\mathrm{B}}_{20}^{-}$, ${\mathrm{B}}_{24}^{-}$, and ${\mathrm{B}}_{28}^{-}$) can simultaneously have helical molecular orbitals and helical spin densities; these seem to be the first compounds discovered to have this intriguing property. We show that chiral Jahn–Teller distortion of quasi-planar boron clusters drives the formation of the helical molecular spin densities in these clusters and show that elongation/enhancement in helical molecular orbitals can be achieved by simply adding more building blocks via a linker. Aromaticity of these boron clusters is discussed. Chiral boron clusters may find potential applications in spintronics, such as molecular magnets. Full article

Orbital angular momentum (OAM) encoding is a promising technique to boost data transmission capacity in optical communications. Most recently, azobenzene films have gained attention as a versatile tool for creating and altering OAM-carrying beams. Unique features of azobenzene films make it possible to control molecular alignment through light-induced isomerization about the azo bond. This feature enables the fabrication of diffractive optical devices such as spiral phase plates and holograms by accurately imprinting a phase profile on the incident light. By forming azobenzene sheets into diffractive optical elements, such as spiral phase plates, one can selectively create OAM-carrying beams. Due to the helical wavefront and phase variation shown by these beams, multiple distinct channels can be encoded within a single optical beam. This can significantly increase the data transmission capacity of optical communication systems with this OAM multiplexing technique. Additionally, holographic optical components made from azobenzene films can be used to build and reconstruct intricate wavefronts. It is possible to create OAM-based holograms by imprinting holographic designs on azobenzene films, which makes it simpler to control and shape optical beams for specific communication requirements. In addition, azobenzene-based materials can then be suitable for integration into optical communication devices because of their reconfigurability, compactness, and infrastructure compatibility, which are the main future perspectives for achieving OAM-based technologies for the next generation, among other factors. In this paper, we see the possible use of azobenzene films in the generation and modification of OAM beams for optical communications through light-induced isomerization. In addition, the potential role of azobenzene films in the development of novel OAM-based devices that paves the way for the realization of high-capacity, OAM-enabled optical communication networks are discussed. Full article

1,3-butadiynamides—the ethynylogous variants of ynamides—receive considerable attention as precursors of complex molecular scaffolds for organic and heterocyclic chemistry. The synthetic potential of these C4-building blocks reveals itself in sophisticated transition-metal catalyzed annulation reactions and in metal-free or silver-mediated HDDA (Hexa-dehydro-Diels–Alder) cycloadditions. 1,3-Butadiynamides also gain significance as optoelectronic materials and in less explored views on their unique helical twisted frontier molecular orbitals (Hel-FMOs). The present account summarizes different methodologies for the synthesis of 1,3-butadiynamides followed by the description of their molecular structure and electronic properties. Finally, the surprisingly rich chemistry of 1,3-butadiynamides as versatile C4-building blocks in heterocyclic chemistry is reviewed by compiling their exciting reactivity, specificity and opportunities for organic synthesis. Besides chemical transformations and use in synthesis, a focus is set on the mechanistic understanding of the chemistry of 1,3-butadiynamides—suggesting that 1,3-butadiynamides are not just simple alkynes. These ethynylogous variants of ynamides have their own molecular character and chemical reactivity and reflect a new class of remarkably useful compounds. Full article

Herein, we describe the synthesis, crystal structure, and electronic properties of {[K₂(dmso)(H₂O)₅][Ni₂(H₂mpba)₃]·dmso·2H₂O}_n (1) and [Ni(H₂O)₆][Ni₂(H₂mpba)₃]·3CH₃OH·4H₂O (2) [dmso = dimethyl sulfoxide; CH₃OH = methanol; and H₄mpba = 1,3-phenylenebis(oxamic acid)] bearing the [Ni₂(H₂mpba)₃]²⁻ helicate, hereafter referred to as {Ni^II₂}. SHAPE software calculations indicate that the coordination geometry of all the Ni^II atoms in 1 and 2 is a distorted octahedron (O_h) whereas the coordination environments for K1 and K2 atoms in 1 are Snub disphenoid J84 (D_2d) and distorted octahedron (O_h), respectively. The {Ni^II₂} helicate in 1 is connected by K⁺ counter cations yielding a 2D coordination network with sql topology. In contrast to 1, the electroneutrality of the triple-stranded [Ni₂(H₂mpba)₃] ²⁻ dinuclear motif in 2 is achieved by a [Ni(H₂O)₆]²⁺ complex cation, where the three neighboring {Ni^II₂} units interact in a supramolecular fashion through four R₂²(10) homosynthons yielding a 2D array. Voltammetric measurements reveal that both compounds are redox active (with the Ni^II/Ni^I pair being mediated by OH^– ions) but with differences in formal potentials that reflect changes in the energy levels of molecular orbitals. The Ni^II ions from the helicate and the counter-ion (complex cation) in 2 can be reversibly reduced, resulting in the highest faradaic current intensities. The redox reactions in 1 also occur in an alkaline medium but at higher formal potentials. The connection of the helicate with the K⁺ counter cation has an impact on the energy levels of the molecular orbitals; this experimental behavior was further supported by X-ray absorption near-edge spectroscopy (XANES) experiments and computational calculations. Full article

The general mechanism of controlling, information and organization in biological systems is based on the internal coherent electromagnetic field. The electromagnetic field is supposed to be generated by microtubules composed of identical tubulin heterodimers with periodic organization and containing electric dipoles. We used a classical dipole theory of generation of the electromagnetic field to analyze the space–time coherence. The structure of microtubules with the helical and axial periodicity enables the interaction of the field in time shifted by one or more periods of oscillation and generation of coherent signals. Inner cavity excitation should provide equal energy distribution in a microtubule. The supplied energy coherently excites oscillators with a high electrical quality, microtubule inner cavity, and electrons at molecular orbitals and in ‘semiconduction’ and ‘conduction’ bands. The suggested mechanism is supposed to be a general phenomenon for a large group of helical systems. Full article

We studied supramolecular chirality induced by circularly polarized light. Photoresponsive azopolymers form a helical intermolecular network. Furthermore, studies on photochemical materials using optical vortex light will also attract attention in the future. In contrast to circularly polarized light carrying spin angular momentum, an optical vortex with a spiral wave front and carrying orbital angular momentum may impart torque upon irradiated materials. In this review, we summarize a few examples, and then theoretically and computationally deduce the differences in spin angular momentum and orbital angular momentum depending on molecular orientation not on, but in, polymer films. UV-vis absorption and circular dichroism (CD) spectra are consequences of electric dipole transition and magnetic dipole transition, respectively. However, the basic effect of vortex light is postulated to originate from quadrupole transition. Therefore, we explored the simulated CD spectra of azo dyes with the aid of conventional density functional theory (DFT) calculations and preliminary theoretical discussions of the transition of CD. Either linearly or circularly polarized UV light causes the trans–cis photoisomerization of azo dyes, leading to anisotropic and/or helically organized methyl orange, respectively, which may be detectable by CD spectroscopy after some technical treatments. Our preliminary theoretical results may be useful for future experiments on the irradiation of UV light under vortex. Full article

The helical distribution of the electronic density in chiral molecules, such as DNA and bacteriorhodopsin, has been suggested to induce a spin–orbit coupling interaction that may lead to the so-called chirality-induced spin selectivity (CISS) effect. Key ingredients for the theoretical modelling are, in this context, the helically shaped potential of the molecule and, concomitantly, a Rashba-like spin–orbit coupling due to the appearance of a magnetic field in the electron reference frame. Symmetries of these models clearly play a crucial role in explaining the observed effect, but a thorough analysis has been largely ignored in the literature. In this work, we present a study of these symmetries and how they can be exploited to enhance chiral-induced spin selectivity in helical molecular systems. Full article

The effect of the polymer chain topology structure on the adsorption behavior in the polymer-nanoparticle (NP) interface is investigated by employing coarse-grained molecular dynamics simulations in various polymer-NP interaction and chain stiffness. At a weak polymer-NP interaction, ring chain with a closed topology structure has a slight priority to occupy the interfacial region than linear chain. At a strong polymer-NP interaction, the “middle” adsorption mechanism dominates the polymer local packing in the interface. As the increase of chain stiffness, an interesting transition from ring to linear chain preferential adsorption behavior occurs. The semiflexible linear chain squeezes ring chain out of the interfacial region by forming a helical structure and wrapping tightly the surface of NP. In particular, this selective adsorption behavior becomes more dramatic for the case of rigid-like chain, in which 3D tangent conformation of linear chain is absolutely prior to the 2D plane orbital structure of ring chain. The local packing and competitive adsorption behavior of bidisperse matrix in polymer-NP interface can be explained based on the adsorption mechanism of monodisperse (pure ring or linear) case. These investigations may provide some insights into polymer-NP interfacial adsorption behavior and guide the design of high-performance nanocomposites. Full article