This tutorial review is addressed to readers with a background in basic organic chemistry and spectroscopy, but without a specific knowledge of electronic circular dichroism. It describes the fundamental principles, instrumentation, data analysis, and different approaches for interpretation of ECD. The discussion focuses on the application of ECD, also in combination with other methods, in structural analysis of organic compounds, including host-guest complexes, and will emphasize the importance of the interplay between configurational and conformational factors. The tutorial also covers modern supramolecular aspects of ECD and recent developments in computational methods.
Chiral π-conjugated molecules provide new materials with outstanding features for current and perspective applications, especially in the field of optoelectronic devices. In thin films, processes such as charge conduction, light absorption, and emission are governed not only by the structure of the individual molecules but also by their supramolecular structures and intermolecular interactions to a large extent. Electronic circular dichroism, ECD, and its emission counterpart, circularly polarized luminescence, CPL, provide tools for studying aggregated states and the key properties to be sought for designing innovative devices. In this review, we shall present a comprehensive coverage of chiroptical properties measured on thin films of organic π-conjugated molecules. In the first part, we shall discuss some general concepts of ECD, CPL, and other chiroptical spectroscopies, with a focus on their applications to thin film samples. In the following, we will overview the existing literature on chiral π-conjugated systems whose thin films have been characterized by ECD and/or CPL, as well other chiroptical spectroscopies. Special emphasis will be put on systems with large dissymmetry factors (g abs and g lum) and on the application of ECD and CPL to derive structural information on aggregated states.
Quantum-mechanical calculations of chiroptical properties have rapidly become the most popular method for assigning absolute configurations (AC) of organic compounds, including natural products. Black-box time-dependent Density Functional Theory (TDDFT) calculations of electronic circular dichroism (ECD) spectra are nowadays readily accessible to nonexperts. However, an uncritical attitude may easily deliver a wrong answer. We present to the Chirality Forum a discussion on what can be called good computational practice in running TDDFT ECD calculations, highlighting the most crucial points with several examples from the recent literature. Chirality 28:466-474, 2016. © 2016 Wiley Periodicals, Inc.
The electronic circular dichroism (ECD) spectra of flexible molecules include the contributions of all conformers populated at the working temperature. ECD spectra of chiral substrates depend on their stereochemistry in terms of both absolute configuration, as reflected in the sign of the spectrum, and molecular conformation, which dictates the overall spectral shape (possibly including the sign) in a very sensitive manner. The unique high sensitivity of ECD towards conformation, as well as of other chiroptical spectroscopies, renders these techniques a useful alternative or complement to standard spectroscopic tools for conformational investigations, such as NMR. This tutorial review provides first a brief discussion of the main principles of ECD spectroscopy and related methods for interpretation of spectra, with special reference to conformational aspects. The review focuses on the common problems encountered in the application of ECD for assignments of absolute configuration of flexible molecules. These problems can be handled either by taking into account the whole conformational ensemble or by considering rigid derivatives prepared ad hoc. Finally, the review presents the relatively less common but very interesting application of ECD spectroscopy for conformational analyses of organic compounds.
The method employing dimolybdenum tetraacetate for the assignment of the absolute configuration of optically active 1,2-diols is thoroughly revisited and applied to several compounds, some of which were synthesized by asymmetric cis-dihydroxylation. No exceptions were found to the empirical rule relating the sign of the induced CD spectrum and the configuration of the substrate, whatever its structure and sterical requirements. To broaden the scope of the method, its applicability to critical situations commonly encountered with synthetic products is tested. It is demonstrated that the method can be applied on samples with low chemical and optical purity, and that it may lend itself as a means to estimate the ee. The roles of the water content of the sample and of the diol-to-dimolybdenum ratio are investigated.
Chiral supramolecular architectures constitute crucial structural and functional elements in living systems and have been long mimicked by chemists to synthesize new artificial systems endowed with desired properties and functions. Among several techniques to study noncovalent chiral assemblies or aggregates, electronic circular dichroism (ECD) plays a key role because many mechanisms responsible for the appearance of ECD bands occur through space, and therefore are intrinsically sensitive to intermolecular interactions, from short to long-range. The aim of this tutorial review is to emphasize the different kinds of information which can be obtained specifically when chiral supramolecular species are characterized by means of ECD spectroscopy. We will survey several typical applications of ECD in the context of supramolecular chemistry, ranging from the simple detection of chiral aggregates or complexes, to the definition of stoichiometric ratios between the partners, the derivation of thermodynamic and kinetic parameters such as binding and rate constants, and ultimately to the refinement of the most plausible structure of the supramolecular species.
The dihedral angle θ of 1,1‘-binaphthyl derivatives is quantitatively related to the wavelength splitting Δλmax of the 220 nm couplet of the CD spectra. This relation is almost independent of measurement conditions (solvent, concentration). Its reliability has been quite successfully tested on about 10 compounds derived from 2,2‘-dimethyl-1,1‘-binaphthyl. A simple and versatile method for the conformational assessment of this class of compounds is reported.
Blennolides A-G (2-8), seven unusual chromanones, were isolated together with secalonic acid B (1) from Blennoria sp., an endophytic fungus from Carpobrotus edulis. This is the first reported isolation of the blennolides 2 and 3 (hemisecalonic acids B and E), the existence of which as the monomeric units of the dimeric secalonic acids had long been postulated. A compound of the proposed structure 4 (beta-diversonolic ester) will need to be revised, as its reported data do not fit those of the established structure of blennolide C (4). Other monomers, the blennolides D-F (5-7) seem to be derived from blennolides A (2) and B (3) by rearrangement of the hydroaromatic ring. The heterodimer 8, composed of the monomeric blennolide A (2) and the rearranged 11-dehydroxy derivative of blennolide E (6), extends the ergochrome family with an ergoxanthin type of skeleton. The structures of the new compounds were elucidated by detailed spectroscopic analysis and further confirmed by an X-ray diffraction study of a single crystal of 2. The absolute configurations were determined by TDDFT calculations of CD spectra, including the solid-state CD/TDDFT approach. Preliminary studies showed strong antifungal and antibacterial activities of these compounds against Microbotryum violaceum and Bacillus megaterium, respectively. They were also active against the alga Chlorella fusca and the bacterium Escherichia coli.
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