Chiral Channels Research Articles

Synthesis, characterization and X-ray crystal structures of two non-molecular coordination polymers of manganese(II) and copper(II) with N-(2-pyridylmethyl)-l-alanine and isothiocyanato ligands

The reduced Schiff base, N-(2-pyridylmethyl)-l-alanine (Pyala), has been prepared and used as a ligand for the synthesis of two new non-centrosymmetrical isothiocyanate mixed-ligand coordination polymers, [MnPyalaSCN] n and [CuPyalaSCN] n . Pyala and the metal complexes were characterized by physico-chemical and spectroscopic methods. The single-crystal X-ray structures of the complexes reveal both compounds to be non-molecular coordination polymers which crystallize in the orthorhombic system. The ligand acts as a bridge between two metal centres in both compounds, forming two six-membered rings around each Mn atom and two five-membered rings around each Cu centre. The 1D chains are assembled via N–H⋯O, N–H⋯S hydrogen bonds and S–S interactions building 3D helical supramolecular networks in both compounds. Packing of the polymers of both compounds along the b-axis gives chiral channels.

Reprint of : Effect of incoherent scattering on three-terminal quantum Hall thermoelectrics

A three-terminal conductor presents peculiar thermoelectric and thermal properties in the quantum Hall regime: it can behave as a symmetric rectifier and as an ideal thermal diode. These properties rely on the coherent propagation along chiral edge channels. We investigate the effect of breaking the coherent propagation by the introduction of a probe terminal. It is shown that chiral effects not only survive the presence of incoherence but they can even improve the thermoelectric performance in the totally incoherent regime.

Reprint of : Time dependent electronic transport in chiral edge channels

We study time dependent electronic transport along the chiral edge channels of the quantum Hall regime, focusing on the role of Coulomb interaction. In the low frequency regime, the a.c. conductance can be derived from a lumped element description of the circuit. At higher frequencies, the propagation equations of the Coulomb coupled edge channels need to be solved. As a consequence of the interchannel coupling, a charge pulse emitted in a given channel fractionalized in several pulses. In particular, Coulomb interaction between channels leads to the fractionalization of a charge pulse emitted in a given channel in several pulses. We finally study how the Coulomb interaction, and in particular the fractionalization process, affects the propagation of a single electron in the circuit. All the above-mentioned topics are illustrated by experimental realizations.

Reprint of : Correlated voltage probe model of relaxation in two Coulomb-coupled edge channels

A phenomenological correlated voltage probe model is introduced to mimic the effects of inelastic scattering between particles in different conduction channels of a phase coherent conductor. As an illustration, the non-equilibrium distribution functions of two noisy co-propagating chiral edge channels of the integer quantum Hall effect are calculated and compared with recent experiments. The method is further applied to calculate the linear response current noise through an interacting Mach–Zehnder interferometer.

Quantum oscillations in Weyl and Dirac semimetal ultrathin films

We show that a thin film of Weyl or Dirac semimetal with a strong in-plane magnetic field becomes a novel two-dimensional Fermi liquid with interesting properties. The Fermi surface in this system is strongly anisotropic, which originates from a combination of chiral bulk channels and the Fermi arcs. The area enclosed by the Fermi surface depends strongly on the in-plane magnetic field component parallel to the Weyl/Dirac node splitting, which leads to unusual behavior in quantum oscillations when the magnetic field is tilted out of the plane. We estimate the oscillation frequencies and the regimes where such effects could be seen in Cd$_3$As$_2$, Na$_3$Bi, and TaAs.

A chiral lanthanide metal-organic framework for selective sensing of Fe(iii) ions.

A new luminescent lanthanide metal-organic framework was synthesized under hydrothermal conditions by introducing the tetracarboxylic acid ligand (H4bptc) as a chromophore to sensitize the luminescence of the Tb(3+) ion. Interestingly, despite the achiral nature of H4bptc, the resulting framework exhibited rare chiral helical channels. The luminescence studies revealed that this material showed a highly selective fluorescence quenching response to Fe(3+) ions in liquid suspension, which can be conveniently observed by the naked eye under UV light. Thus, this material can be potentially used as a chemosensor for sensing Fe(3+) ions and its selective luminescence quenching response can be explained in terms of the competitive absorption mechanism.

One-dimensional edge state transport in a topological Kondo insulator

Topological insulators, with metallic boundary states protected against time-reversal-invariant perturbations, are a promising avenue for realizing exotic quantum states of matter including various excitations of collective modes predicted in particle physics, such as Majorana fermions and axions. According to theoretical predictions, a topological insulating state can emerge from not only a weakly interacting system with strong spin-orbit coupling, but also in insulators driven by strong electron correlations. The Kondo insulator compound SmB6 is an ideal candidate for realizing this exotic state of matter, with hybridization between itinerant conduction electrons and localized $f$-electrons driving an insulating gap and metallic surface states at low temperatures. Here we exploit the existence of surface ferromagnetism in SmB6 to investigate the topological nature of metallic surface states by studying magnetotransport properties at very low temperatures. We find evidence of one-dimensional surface transport with a quantized conductance value of $e^2/h$ originating from the chiral edge channels of ferromagnetic domain walls, providing strong evidence that topologically non-trivial surface states exist in SmB6.

Helical Channel Mesoporous Materials with Embedded Magnetic Iron Nanoparticles: Chiral Recognition and Implications in Asymmetric Olefin Epoxidation

AbstractIn this work a mesoporous nanocomposite material comprising helical chiral channels and with embedded magnetic iron oxide nanoparticles in its Si‐based MCM‐41 type framework was synthesized. Afterwards, a bipyridine derivative was grafted to the inner surface used as ligand to coordinate a molybdenum(II) precursor complex. The Mo loading was found to be 2.42 wt% Mo, corresponding to 0.26 mmolMo g−1. The successful preparation of this helical mesoporous material was evidenced by an extensive characterization process using powder XRD, SEM/TEM analysis, FT‐IR and Raman spectroscopies, TGA analysis and also by SQUID measurements. Selective adsorption of enantiopure D‐ and L‐phenylalanine shows that the material has a preference for the D‐ over the L‐ enantiomer. This provides evidence that the channels are chiral (although the particles are not) and that it is useful for chiral recognition applications. It also sets the explanation to the good results achieved in the selective epoxidation of olefins. The resulting material was tested as catalytic precursor in the epoxidation of cis‐cyclooctene, styrene, R‐(+)‐limonene and trans‐hex‐2‐en‐1‐ol, using tert‐butyl hydroperoxide (tbhp) as oxygen source. The catalytic studies show that the synthesized material yields selectively the desired epoxides of the tested substrates with very good results, especially at higher temperatures and using toluene as solvent. The major achievement of the catalyst was an outstanding stereocontrol of the reaction products imposed by the confined space of the helical chiral channels. Therefore these materials offer an important contribution to asymmetric catalysis and to fields where chiral recognition is a relevant concept.magnified image

Time dependent electronic transport in chiral edge channels

We study time dependent electronic transport along the chiral edge channels of the quantum Hall regime, focusing on the role of Coulomb interaction. In the low frequency regime, the a.c. conductance can be derived from a lumped element description of the circuit. At higher frequencies, the propagation equations of the Coulomb coupled edge channels need to be solved. As a consequence of the interchannel coupling, a charge pulse emitted in a given channel fractionalized in several pulses. In particular, Coulomb interaction between channels leads to the fractionalization of a charge pulse emitted in a given channel in several pulses. We finally study how the Coulomb interaction, and in particular the fractionalization process, affects the propagation of a single electron in the circuit. All the above-mentioned topics are illustrated by experimental realizations.

An edge-magnetoplasmon Mach-Zehnder interferometer

We report an edge-magnetoplasmon (EMP) Mach-Zehnder (MZ) interferometer in a quantum Hall system. The MZ interferometer, which is based on the interference of two EMP beams traveling in chiral one-dimensional edge channels, is constructed by tailoring edge channels with functional devices such as splitters and delay lines. We measured 1 GHz EMP beams transmitted through the interferometer while tuning the phase evolution along two interference paths using tunable delay lines. Clear interference patterns as a function of the phase difference ensure the MZ interference. Moreover, the MZ interferometry is applied to evaluate the EMP transport through an attenuator interposed in one of the paths. This technique will be useful for investigating the functionalities of devices in plasmonics.

Preparation and characterization of Ni2(mal)2(bpy) homochiral MOF membrane

AbstractAs an important subclass of metal‐organic frameworks (MOFs), homochiral MOFs show special ability of asymmetric catalysis and enantioselective separation via the open chiral channels or cavities. A new homochiral MOF membrane [Ni2(mal)2(bpy)]•2H2O (Ni‐MB) was synthesized by a secondary growth technique, in which high energy ball milling was employed to prepare nanosized MOF seeds, and their synthesis condition were optimized. X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), and thermal gravimetric analysis were used to measure physicochemical properties of the MOF crystals and membranes. In particular, the homochiral MOF membranes were characterized by nano‐indentation/scratch technique with high‐resolution mechanical property analysis. The SEM results indicated that the membrane was continuous and integrated without observable defects; the permeation measurements of single gas show that the permeate flux of nitrogen was independent on the transmembrane pressure, further confirming the absence of macroporous defects in the as‐prepared chiral MOF membranes. It is expected that the proposed chiral MOF membrane can be potentially applied to enantioselective separation in the future. © 2015 Curtin University of Technology and John Wiley & Sons, Ltd.

Structural Insight into Guest Binding Sites in a Porous Homochiral Metal-Organic Material.

An enantiomeric pair of chiral metal-organic materials (CMOMs) based upon mandelate (man) and 4,4'-bipyridine (bpy) ligands, [Co2(S-man)2(bpy)3](NO3)2·guest (1S·guest) and [Co2(R-man)2(bpy)3](NO3)2·guest (1R·guest), have been prepared. The cationic frameworks exhibit one-dimensional chiral channels with dimensions of 8.0 Å × 8.0 Å. The pore chemistry is such that chiral surfaces lined with nitrate anions and phenyl groups create multiple binding sites for guest and/or solvent molecules. The performance of 1S and 1R with respect to resolution of racemic mixtures of 1-phenyl-1-propanol (PP) was studied by varying time, temperature, and the use of additives. Selectivity toward PP was determined by chiral HPLC with ee values of up to 60%. The binding sites and host-guest interactions were investigated through single-crystal X-ray structural analyses of guest-exchanged 1S and 1R. Crystallographically observed structural changes (e.g., the absolute configurations of the three PP binding sites switch from R, R, and S to R, R, and R/S) correlate with experimentally observed ee values of 33% and 60% for variants of 1S that contain PP and different solvent molecules, 1S·PPex and 1S·PPex', respectively. The fact that manipulation of guest solvent molecules, which in effect serve as cofactors, can modify chiral sites and increase enantioselectivity is likely to aid in the design of more effective CMOMs and processes for chiral separations.

Correlated voltage probe model of relaxation in two Coulomb-coupled edge channels

A phenomenological correlated voltage probe model is introduced to mimic the effects of inelastic scattering between particles in different conduction channels of a phase coherent conductor. As an illustration, the non-equilibrium distribution functions of two noisy co-propagating chiral edge channels of the integer quantum Hall effect are calculated and compared with recent experiments. The method is further applied to calculate the linear response current noise through an interacting Mach–Zehnder interferometer.

Effect of incoherent scattering on three-terminal quantum Hall thermoelectrics

A three-terminal conductor presents peculiar thermoelectric and thermal properties in the quantum Hall regime: it can behave as a symmetric rectifier and as an ideal thermal diode. These properties rely on the coherent propagation along chiral edge channels. We investigate the effect of breaking the coherent propagation by the introduction of a probe terminal. It is shown that chiral effects not only survive the presence of incoherence but they can even improve the thermoelectric performance in the totally incoherent regime.

Zero-Field Dissipationless Chiral Edge Transport and the Nature of Dissipation in the Quantum Anomalous Hall State.

The quantum anomalous Hall (QAH) effect is predicted to possess, at a zero magnetic field, chiral edge channels that conduct a spin polarized current without dissipation. While edge channels have been observed in previous experimental studies of the QAH effect, their dissipationless nature at a zero magnetic field has not been convincingly demonstrated. By a comprehensive experimental study of the gate and temperature dependences of local and nonlocal magnetoresistance, we unambiguously establish the dissipationless edge transport. By studying the onset of dissipation, we also identify the origin of dissipative channels and clarify the surprising observation that the critical temperature of the QAH effect is 2 orders of magnitude smaller than the Curie temperature of ferromagnetism.

Perfect valley filter in a topological domain wall

We propose a realization of perfect valley filters based on the chiral domain-wall channels between a quantum anomalous Hall insulator and a quantum valley Hall insulator. Uniquely, all these channels reside in the same valley and propagate unidirectionally, $100\%$ valley-polarizing passing-by carriers without backscattering. The valley index, the chirality, and the number of the channels are protected by topological charges, controllable by external fields, and detectable by circular dichroism.

Polarized Water Wires under Confinement in Chiral Channels.

The alignment of water molecules along chiral pores may activate proton/ion conduction along dipolar hydrophilic pathways. Here we show that a simple synthetic "T-channel" forms a directional pore with its carbonyl moieties solvated by chiral helical water wires. Atom-scale simulations and experimental crystallographic assays reveal a dynamical structure of water and electrolyte solutions (alkali metal chlorides) confined in these organic T-channels. Oscillations in the dipole orientation, which correspond to alternative ordering (dipole up-dipole down) of the water molecules with a period of about 4.2 Å (imposed by the distance between two successive carbonyl groups) are observed. When ions are added to the system, despite the strong Coulombic water/ion interaction, confined water remains significantly ordered in the T-channel and still exhibits surface-induced polarization. Cation permeation can be achieved through alternated hydration-dehydration occurring along strongly oriented water wires. The T-channel, which exhibits chirality with strong water orientation, provides an opportunity to unravel novel water-channel systems that share many interesting properties of biomolecular systems.

Homochiral Metal–Organic Framework with Intrinsic Chiral Topology and Helical Channels

Presented here is an unusual microporous metal–organic framework (FIR-30) integrating helical channels, intrinsical chirality, and permanent porosity. The structure of FIR-30 containing three types of cages has two interpenetrating helical channel systems with opposite handedness, which can be considered a surface with the same topology as gyroid, and the generation of chirality is related with the intrinsically chiral topology of FIR-30. The results provide new insight toward the construction of chiral MOFs with helical channels.

Step-by-step strategy from achiral precursors to polyoxometalates-based chiral organic-inorganic hybrids.

Using two types of triol ligands, several novel asymmetrically triol-functionalized Anderson organic hybrids have been efficiently synthesized in high purity and good yields via a convenient two-step esterification reaction. These organic-inorganic hybrids are chiral and can be spontaneously resolved with suitable solvents. Their molecular and crystal structures have been confirmed by single-crystal X-ray diffraction studies. Stable solid-state chirality of the corresponding enantiopure crystals has also been confirmed definitively by CD spectra. Interestingly, these organic-inorganic hybrids possess a layer-by-layer structure, forming solvent-accessible nanoscale chiral channels via a 1D infinite helical chain substructure. TGA measurements indicated that the species of the central heteroatoms significantly effects the stability of these compounds.

A New Chiral Coordination Polymer with Large Cavities of [Cu3(NA)6(DMF)3]n: Synthesis, Structural and Magnetic Property

A new metal–organic architectures, [Cu3(NA)6(DMF)3]n (1), where NA stands for nicotinic acid, has been successfully synthesized and characterized by elemental analysis, IR, TG analysis and single crystal X-ray diffraction. Single-crystal X-ray diffraction reveals that the CuII centers adopt a distorted square pyramidal geometry, and nicotinic acid acts as a bidentate ligand connected with the adjacent two Cu atoms by the pyridyl and carboxylate groups to form a 3D framework structure. The framework exhibits open chiral channels with coordinated DMF molecules inside it. In addition, the magnetic properties have also been studied.