Search results for "chirality"
showing 10 items of 188 documents
Vibrational circular dichroism studies of exceptionally strong chirality inducers in liquid crystals.
2021
7,7′-Disubstituted 2,2′-methylenedioxy-1,1′-binaphthyls are highly efficient chirality inducers in nematic liquid crystals. The absolute configuration of these compounds is, however, hard to determine as they only crystallize as racemic mixtures. In this work a Vibrational Circular Dichroism (VCD) study is reported that provides an unambiguous determination of the absolute configuration of these compounds. An in-depth General Coupled Oscillator (GCO) analysis of the source of the VCD signal reveals that the unusual structure of these binaphthyl compounds inherently leads to strong and robust VCD bands. Combined with linear transit calculations, our VCD studies allow for the determination of…
Vibrational circular dichroism spectroscopy for probing the expression of chirality in mechanically planar chiral rotaxanes
2020
Mechanically interlocked molecules can exhibit molecular chirality that arises due to the mechanical bond rather than covalent stereogenic units. Developing applications of such systems is made challenging by the absence of techniques for assigning the absolute configuration of products and methods to probe how the mechanical stereogenic unit influences the spatial arrangements of the functional groups in solution. Here we demonstrate for the first time that Vibrational Circular Dichroism (VCD) can be used to not only discriminate between mechanical stereoisomers but also provide detailed information on their (co)conformations. The latter is particularly important as these molecules are now…
Design of Magnetic Coordination Polymers Built from Polyoxalamide Ligands: A Thirty Year Story
2018
International audience; The aim of this review is to pay tribute to the legacy of O. Kahn. Kahn's credo was to synthesize magnetic compounds with predictable structure and magnetic properties. This is illustrated herein with results obtained by Kahn's group during his Orsay period thirty years ago, but also on the basis of our recent results on the synthesis of coordination polymers with oxamate ligands. The first part of this review is devoted to a short description of the necessary knowledge in physics and theoretical chemistry that Kahn and his group have used to select oxamate ligands, the complex‐as‐ligand strategy and the synthesis of heterobimetallic systems. Then, we describe the st…
Diastereoselective formation of homochiral flexible perylene bisimide cyclophanes and their hybrids with fullerenes†‡
2021
Cyclophanes of different ring sizes featuring perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) linked by flexible malonates were designed, synthesized, and investigated with respect to their structural, chemical and photo-physical properties. It is predominantly the number of PBIs and their geometric arrangement, which influence dramatically their properties. For example, two-PBI containing cyclophanes reveal physico-chemical characteristics that are governed by strong co-facial π–π interactions. This is in stark contrast to cyclophanes with either three or four PBIs. Key to co-facial π–π stackings are the flexible malonate linkers, which, in turn, set up the ways and means for diaster…
A theoretical and experimental study of the racemization process of hexaaza[5]helicenes
2014
A dynamic 1H NMR study, together with DFT calculations, of bis-([1,2,3]triazolo)[1,5-a:5′,1′-k][1,10]phenanthroline 2 has allowed to identify the ring and open forms of a new example of ring/chain tautomerism, as well as their interconversion barriers (ring/ring and ring/open). The barrier of the exchange process between the chain forms and the ring form was found higher than the 'racemization' process in the closed form, so the ring opening does not contribute to the 'racemization'. The di-1,10-methyl and di-1,10-iodo derivatives have been prepared and their properties calculated.
The Ξ(1620) and Ξ(1690) molecular states from S = −2 meson-baryon interaction up to next-to-leading order
2023
We have studied the meson-baryon interaction in the neutral $S=-2$ sector using an extended Unitarized Chiral Perturbation Theory, which takes into account not only the leading Weinberg-Tomozawa term (as all the previous studies in $S=-2$ sector), but also the Born terms and next-to-leading order contribution. Based on the SU(3) symmetry of the chiral Lagrangian we took most of the model parameters from the BCN model \cite{Feijoo:2018den}, where these were fitted to a large amount of experimental data in the neutral $S=-1$ sector. We have shown that our approach is able to generate dynamically both $\Xi(1620)$ and $\Xi(1690)$ states in very reasonable agreement with the data, and can natura…
Chirality transfer and chiral turbulence in gauge theories
2020
Chirality transfer between fermions and gauge fields plays a crucial role for understanding the dynamics of anomalous transport phenomena such as the Chiral Magnetic Effect. In this proceeding we present a first principles study of these processes based on classical-statistical real-time lattice simulations of strongly coupled QED $(e^2N_f=64)$. Our simulations demonstrate that a chirality imbalance in the fermion sector triggers chiral plasma instabilities in the gauge field sector, which ultimately lead to the generation of long range helical magnetic fields via a self-similar turbulent cascade of the magnetic helicity.
No chiral light bending by clumps of axion-like particles
2019
We study the propagation of light in the presence of a parity-violating coupling between photons and axion-like particles (ALPs). Naively, this interaction could lead to a split of light rays into two separate beams of different polarization chirality and with different refraction angles. However, by using the eikonal method we explicitly show that this is not the case and that ALP clumps do not produce any spatial birefringence. This happens due to non-trivial variations of the photon's frequency and wavevector, which absorb time-derivatives and gradients of the ALP field. We argue that these variations represent a new way to probe the ALP-photon couping with precision frequency measuremen…
Absolute Chiral Sensing in Dielectric Metasurfaces Using Signal Reversals.
2020
Sensing molecular chirality at the nanoscale has been a long-standing challenge due to the inherently weak nature of chiroptical signals, and nanophotonic approaches have proven fruitful in accessing these signals. However, in most cases, absolute chiral sensing of the total chiral refractive index has not been possible, while the strong inherent signals from the nanostructures themselves obscure the weak chiroptical signals. Here, we propose a dielectric metamaterial system that overcomes these limitations and allows for absolute measurements of the total chirality, and the possibility for a crucial signal reversal that enables chirality measurements without the need for sample removal. As…