Straightforward synthesis and resolution of a series of chiral fluorescent macrocycles are presented, together with their electronic circular dichroism (ECD), strong excimer fluorescence (EF, λ 300 to 650 nm) and allied highly circularly polarized luminescence (CPL, g_lum up to 1.7 × 10⁻²). The ECD, EF and CPL responses are strongly affected by the presence of metal ions (Na⁺, Ba²⁺) thanks to deep conformational changes. While ECD signals can be almost completely reversibly inverted upon the complexation/decomplexation of metal ions in a typical binary response, CPL signals are reversibly quenched concomitantly. The designed macrocycles display thus a remarkable combination of both +/− ECD and on/off CPL reversible switching.

Background: Quantum mechanical simulations of chiroptical properties, such as electronic circular dichroism (ECD), optical rotation (OR), and vibrational circular dichroism (VCD), have rapidly become very popular to assign the absolute configuration of novel natural products. Objective: We review the application of the ECD/OR/VCD computational methodology to chiral metabolites of fungal origin. First, we summarize the fundamentals of the three spectroscopies; then, we focus on the specific experimental and computational issues allied to the application of their calculations. Methods: We surveyed the entire literature describing the use of ECD/OR/VCD computations for fungal metabolites, and catalogued all papers according to the method employed and to the structural family of compounds. Then, we chose several examples to illustrate the use of the techniques and highlight the practical application of the computational approach. Results: Our literature survey demonstrates that the simulation of ECD/OR/VCD spectra is nowadays widespread and accessible also to non-experts, although a good computational practice is necessary to avoid wrong assignments. ECD is still the most common technique used in the context of fungal metabolites. OR and VCD may be profitably employed when the compound of interest lacks chromophoric groups. Our examples illustrate that the combination of two or more chiroptical methods is strongly advisable in some cases, especially in the presence of high conformational flexibility, where a single technique does not lead to a safe conclusion. Conclusion: The ECD/OR/VCD computational approach is a reliable and versatile method to assign the absolute configuration of fungal metabolites and related natural products.

We studied enantiopure chiral trivalent lanthanide (Ln³⁺ = La³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Tm³⁺, and Yb³⁺) complexes with two fluorinated achiral tris(β-diketonate) ligands (HFA = hexafluoroacetylacetonate and TTA = 2-thenoyltrifluoroacetonate), incorporating a chiral bis(oxazolinyl)pyridine (PyBox) unit as a neutral ancillary ligand, by the combined use of optical and chiroptical methods, ranging from UV to IR both in absorption and circular dichroism (CD), and including circularly polarized luminescence (CPL). Ultimately, all the spectroscopic information is integrated into a total and a chiroptical super-spectrum, which allows one to characterize a multidimensional chemical space, spanned by the different Ln³⁺ ions, the acidity and steric demand of the diketone and the chirality of the PyBox ligand. In all cases, the Ln³⁺ ions endow the systems with peculiar chiroptical properties, either allied to f–f transitions or induced by the metal onto the ligand. In more detail, we found that Sm³⁺ complexes display interesting CPL features, which partly superimpose and partly integrate the more common Eu³⁺ properties. Especially, in the context of security tags, the pair Sm/Eu may be a winning choice for chiroptical barcoding.

We highlight the power of electronic circular dichroism imaging (CDi), a technique developed at Diamond Light Source B23 beamline for synchrotron radiation circular dichroism (SRCD) to detect local domains endowed with a chiral supramolecular order in thin films of chiral oligomers and polymers. The highly brilliant and collimated beam light of B23 enabled CDi at a spatial resolution of 0.1 mm, unattainable with benchtop electronic circular dichroism (ECD) spectropolarimeters. CDi is bridging the gap between standard ECD spectroscopy and conventional microscopy. Presently, we apply CDi to reveal the local polymorphism of chiral oligothiophene-based molecules. By extensive use of a post-acquisition data-analysis tool called similarity factor, we quantified the polymorphs revealing a manifold of aggregation pathways whose relative weight was a function of the sample preparation protocol. This work uncovers the parameters that need to be optimised in order to obtain reproducible and controllable supramolecular structures in thin films, which is of paramount importance for materials with optoelectronic properties. It is noteworthy that this analysis is based on CDi measurements at high spatial resolutions of thin films of organic chiral semiconductors at the ultimate stage of preparation as the active layer of an optoelectronic device.