2,339 research outputs found

    Chiroptical studies on brevianamide B : vibrational and electronic circular dichroism confronted

    Get PDF
    Chiroptical spectroscopy, such as electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) are highly sensitive techniques to probe molecular conformation, configuration, solvation and aggregation. Here we report the application of these techniques to study the fungal metabolite brevianamide B. Comparison of the experimental ECD and VCD spectra with the density functional theory (DFT) simulated counterparts establishes that VCD is the more reliable technique to assign absolute configuration due to the larger functional and dispersion dependence of computed ECD spectra. Despite a low amount of available material, and a relatively unusual example of using VCD carbonyl multiplets, the absolute configuration could be reliably predicted, strengthening the case for application of VCD in the study of complex natural products. Spectral and crystallographic evidence for or against the formation of a dimeric aggregate is discussed; in solution the VCD spectra strongly suggest only monomeric species are present

    Chiroptical Spectroscopy of C3 Molecules

    Get PDF
    The relevance of molecules with C3 symmetry comes from the fact of many of them, upon assembling as columnar helical macromolecules, are ideal platform for electro-optical devices, for example as liquid crystals. The properties of these devices are highly dependent of the structure of the bulk aggregates, and consequently they can be controlled by modifying the position and nature of the stereocenters in the molecular building blocks. In this work we present an electronic and vibrational chiroptical study on a series of star-shaped molecules based on the octopolar C3-symmetric 1,3,5-(phenylene-ethynylene)-benzene block.Universidad de Málaga, Campus de Excelencia Internacional Andalucía Tec

    Structure and Properties of Simple and Aggregate Systems by Circular Dichroism Spectroscopy

    Get PDF
    This thesis deals with the investigation of structural properties of many different systems via Electronic Circular Dichroism (ECD). The interpretation of experimental data has been carried out mainly with quantum-chemistry methods, such as Density Functional Theory (DFT), on both solution and solid-state systems. The analysis of solution systems is oriented towards applications on biologically active compounds, both natural or synthetic, and its objective is to underline the key role of these approaches in the determination of the absolute configuration and the difficulties that may be encountered in case of flexible molecules. Solid-state measurements represent an attractive alternative to these cases where a lot of conformations are present, but difficulties in the interpretation of the signals due to solid-state interactions which are not observable in solution may be faced. For a better understanding of spectral lineshapes, more detailed analyses have been performed taking into account vibronic effects, which may also assist in the determination of the conformational situation of the investigated substrate. The limitations of the vibronic treatment for coupled electronic states have been considered, leading to a general all-coordinate approach which allows simulating the electronic spectrum of “dimeric” molecules with weakly coupled electronic states through a time dependent approach

    About Helices and Solvents: VCD and more

    Get PDF
    Intermolecular forces drive self-organization of molecules, which is ultimately the origin of most the physical and chemical phenomena in Nature. Molecules able to interact themselves by non-covalent forces, as hydrogen bonding and/or hydrophobic attractions, usually form macrostructures in condensed phases (solid, solution). The properties of these aggregates depend of three main factors: the structural and chemical features of the molecules, the nature of intermolecular forces and the environment. The first two drive aggregation in solid state, while in solution the role of the solvent become determinant as it can induce a variety of structural effects on the aggregation behaviour of the solute. In the case of chiral molecules, this property is transferred to the aggregates and supramolecular chirality appears. Here we present our research on chiral molecules that self-organize in solution forming helical structures. We use VCD as the main chiroptical tool, but also supported by other chiroptical spectroscopies (ECD, ROA) and theoretical modelling. In our first steps, we studied the effect of modulating the environmental settings on the helices. Thus, helix handedness was proved highly and reversibly dependent on factors as pH or ionic strength in peptide-mimetic hydrogelators. We also observe how the initial conditions (concentration, temperature) were capable of controlling the helix structure of oligo-p-phenylene-based polymers towards kinetic or thermodynamics pathways. Besides, the structure of the helices can also be the consequence of direct solvent-solute interactions. In this way, we have demonstrated that an achiral solvent can act as a template for chiral organization of N-heterotriangulenes-based organogelators, thus showing the different levels of complexity of the hierarchical organization of supramolecular polymers. But the solvent-helix interactions can be bidirectional. As a nice example, we recorded chiral signals which can be only assigned to the organization of the solvent molecules around helical aggregates of phenylglycine functionalized poly(phenylacetylene)s. The solvent molecules thus form a first solvation shell to which the helix chirality is transferred. The helices would act therefore as a template of the solvent molecules, and the chirality of this external helix would be fully controlled by the solute.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech
    • …