A 2D chiral microcavity based on apparent circular dichroism.

Engineering asymmetric transmission between left-handed and right-handed circularly polarized light in planar Fabry-Pérot (FP) microcavities would enable a variety of chiral light-matter phenomena, with applications in spintronics, polaritonics, and chiral lasing. Such symmetry breaking, however, generally requires Faraday rotators or nanofabricated polarization-preserving mirrors. We present a simple solution requiring no nanofabrication to induce asymmetric transmission in FP microcavities, preserving low mode volumes by embedding organic thin films exhibiting apparent circular dichroism (ACD); an optical phenomenon based on 2D chirality. Importantly, ACD interactions are opposite for counter-propagating light. Consequently, we demonstrated asymmetric transmission of cavity modes over an order of magnitude larger than that of the isolated thin film. Through circular dichroism spectroscopy, Mueller matrix ellipsometry, and simulation using theoretical scattering matrix methods, we characterize the spatial, spectral, and angular chiroptical responses of this 2D chiral microcavity.

Triple para-Functionalized Cations and Neutral Radicals of Enantiopure Diaza[4]helicenes.

Modulation of absorbance and emission is key for the design of chiral chromophores. Accessing a series of compounds absorbing and emitting (circularly polarized) light over a wide spectral window and often toward near-infrared is of practical value in (chir)optical applications. Herein, by late-stage functionalization on derivatives bridging triaryl methyl and helicene domains, we have achieved the regioselective triple introduction of para electron-donating or electron-withdrawing substituents. Extended tuning of electronic (e.g., E1/2red -1.50 V → -0.68 V) and optical (e.g., emission covering from 550 to 850 nm) properties is achieved for the cations and neutral radicals; the latter compounds being easily prepared by mono electron reductions under electrochemical or chemical conditions. While luminescence quantum yields can be increased up to 70% in the cationic series, strong Cotton effects are obtained for certain radicals at low energies (λabs ∼ 700-900 nm) with gabs values above 10-3. The open-shell electronic nature of the radicals was further characterized by electron paramagnetic resonance revealing an important spin density delocalization that contributes to their persistence.

Impact of Temperature on the Chiroptical Properties of Thin Films of Chiral Thiophene-based Oligomers.

According to the theoretical model based on the Mueller matrix approach, the experimental electronic circular dichroism (ECD) for thin films of chiral organic dyes can be expressed as the sum of several contributions, two of which are the most significant: 1) an intrinsic component (CDiso) invariant upon sample orientation, reflecting the molecular and/or supramolecular chirality, due to 3D-chiral nanoscopic structures; 2) a non-reciprocal component (LDLB) which inverts its sign upon sample flipping, which arises from the interaction of linear dichroism and linear birefringence in locally anisotropic domains, expression of 2D-chiral micro/mesoscopic structures. In this work, we followed in parallel through ECD and differential scanning calorimetry (DSC) the temperature evolution of the supramolecular arrangements of thin films of five structurally related chiral thiophene-based oligomers with different LDLB/CDiso ratio. By increasing the temperature, regardless of phase transitions observed by DSC analysis, systems with strong CDiso revealed no changes in the ECD spectrum, while compounds with dominant LDLB contribution underwent a gradual (and reversible) reduction of (apparent) ECD signals. These findings demonstrated that the concomitant occurrence of intrinsic and non-reciprocal components in the ECD spectrum of thin films of chiral organic dyes is strictly correlated with solid-state organizations of different stability.

Magnetic Circular Dichroism Elucidates Molecular Interactions in Aggregated Chiral Organic Materials.

Chiral materials formed by aggregated organic compounds play a fundamental role in chiral optoelectronics, photonics and spintronics. Nonetheless, a precise understanding of the molecular interactions involved remains an open problem. Here we introduce magnetic circular dichroism (MCD) as a new tool to elucidate molecular interactions and structural parameters of a supramolecular system. A detailed analysis of MCD together with electronic circular dichroism spectra combined to ab initio calculations unveils essential information on the geometry and energy levels of a self-assembled thin film made of a carbazole di-bithiophene chiral molecule. This approach can be extended to a generality of chiral organic materials and can help rationalizing the fundamental interactions leading to supramolecular order. This in turn could enable a better understanding of structure-property relationships, resulting in a more efficient material design.

Chiral diketopyrrolo[3,4-c]pyrrole-based oligothiophenes: Synthesis and characterization of aggregated states in solution and thin films.

In this work, we synthesized a family of three structurally related chiral oligothiophenes containing a 1,4-diketo-3,6-diarylpyrrolo[3,4-c]pyrrole (DPP) unit as the central core; functionalized with the same (S)-3,7-dimethyl-1-octyl chains on the nitrogen atoms of lactam moieties, they only differ in the number of lateral thiophene units. The aggregation modes of these π-conjugated chiral systems were evaluated by means of UV-Vis absorption and ECD spectroscopies in conditions of solution aggregation (CHCl3 /MeOH mixtures) and as thin films, describing in particular the impact of the π-conjugation length on the chiroptical properties. Interestingly, we found that the variable number of thiophene units attached to the DPP core affects not only the propensity to aggregation but also the aggregates' helicity. ECD revealed information about the supramolecular arrangement of these molecules, that one would not obtain by using conventional optical spectroscopy and microscopy techniques. Thin film samples revealed very different aggregation modes with respect to solution aggregates, casting doubts on the common assumption that these latter may serve as simple models of the former ones.

Negative Nonlinear CD-ee Dependence in Polycrystalline BINOL Thin Films.

Generally, the relationship between the observed circular dichroism and the enantiomeric excess in chiral systems (CD-ee dependence) is linear. While positive nonlinear behavior has often been reported in the past, examples of negative nonlinear (NN) behavior in CD-ee dependence are rare and not well understood. Here, we present a strong NN CD-ee dependence within polycrystalline thin films of BINOL by using second-harmonic-generation circular dichroism (SHG-CD) and commercial CD spectroscopy studies. Theoretical calculations, microscopy, and FTIR studies are employed to further clarify the underlying cause of this observation. This behavior is attributed to the changing supramolecular chirality of the system. Systems exhibiting NN CD-ee dependence hold promise for highly accurate enantiomeric excess characterization, which is essential for the refinement of enantio-separating and -purifying processes in pharmaceuticals, asymmetric catalysis, and chiral sensing. Our findings suggest that a whole class of single-species systems, i.e., racemate crystals, might possess NN CD-ee dependence and thus provide us a vast playground to better understand and exploit this phenomenon.

Enabling Stereochemical Communication and Stimuli-Responsive Chiroptical Properties in Biphenyl-Capped Cyclodextrins.

Chiroptical materials are gaining increasing interest due to their innovative character and their applications in optoelectronics and data encryption technologies. Fully harnessing the potential of building blocks from the "chiral pool", such as native cyclodextrins (CDs), as they often lack chromophores suitable for the construction of materials with significant chiroptical properties. Here, we present the synthesis and characterization of a two-level molecular stack consisting of a point-chiral element (CD) and an axially chiral element (biphenyl), capable of effectively translating the overall stereochemical information contained in CDs into stimuli-responsive chiroptical properties. α- and ß-permethylated CDs were efficiently capped with two different 2,2'-difunctionalized 1,1'-biphenyl units. In CD derivatives containing the rigid 2,2'-dihydroxy-1,1'-biphenyl cap, two intramolecular hydrogen bonds act synergistically as stereoselective actuators, enabling effective communication between the two levels and the transfer of nonchromophoric stereochemical information from the cyclic-oligosaccharide to the atropoisomeric cap. The chiroptical properties can be finely tuned by external stimuli such as temperature and solvent. The way chirality is transferred from the CD platform to the biphenyl cap was revealed thanks to crystallographic and computational analyses, together with electronic circular dichroism (ECD) studies.

2,4,5,7-Tetranitrofluorenone Oximate for the Naked-Eye Detection of H-Bond Donors and the Chiroptical Sensing of Enantiopure Reagents.

Hydrogen bonding greatly influences rates and equilibrium positions of chemical reactions, conformations, and sometimes even stereochemistry. This study reports on tetranitrofluorenone oximate, a novel dye capable of naked-eye detection of hydrogen-bond donating species (HBDs) and of rapid determination of H-bond donation strength by hypsochromic shift monitoring. In addition, the molecule possesses atropisomeric conformations, of M and P configuration, as evidenced in solid and solution state studies by X-ray diffraction and electronic circular dichroism (ECD), respectively. In the latter case, enantiopure bis-thioureas were the most effective HBDs to promote a chiral induction (diastereoselective recognition, Pfeiffer effect); the ECD results being rationalized by time-dependent density functional theory (TDDFT) calculations. Based on these experiments, bis-thioureas were used as chiral reagents in asymmetric 1,3-dipolar cycloadditions of structurally-related nitrones; the ECD sensing of the stereoinduction between bis-thioureas and the oximate serving as an indirect method of selection of the most effective HBD for asymmetric synthesis.

Spatially Resolved Chiroptical Spectroscopies Emphasizing Recent Applications to Thin Films of Chiral Organic Dyes.

Instrumental techniques able to identify and structurally characterize the aggregation states in thin films of chiral organic π-conjugated materials, from the first-order supramolecular arrangement up to the microscopic and mesoscopic scale, are very helpful for clarifying structure-property relationships. Chiroptical imaging is currently gaining a central role, for its ability of mapping local supramolecular structures in thin films. The present review gives an overview of electronic circular dichroism imaging (ECDi), circularly polarized luminescence imaging (CPLi), and vibrational circular dichroism imaging (VCDi), with a focus on their applications on thin films of chiral organic dyes as case studies.

Chiral Diketopyrrolo[3,4-c]pyrrole-1,2,3-1H-triazole Dyes with Highly Tuneable Properties in Solution and Thin Films.

Invited for the cover of this issue are the research groups of Lorenzo Di Bari at the University of Pisa and Gianluca Maria Farinola at the University of Bari Aldo Moro. The image depicts three diketopyrrolo[3,4-c]pyrrole-1,2,3-1H-triazole dyes with the same chiral appendage R* but different achiral substituent groups Y showing profoundly different features in their aggregated form. Read the full text of the article at 10.1002/chem.202300291.

Multistate Aggregation-Induced Chiroptical Properties of Enantiopure Disulfide-Mediated Bispyrene Macrocycles.

A chiral bispyrene macrocycle designed for exclusive intermolecular excimer fluorescence upon aggregation was synthesized by a double hydrothiolation of a bis-enol ether macrocycle followed by intramolecular oxidation of free thiols. Unusually high stereoselectivity was achieved for the thiol-ene additions under templated conditions and Et3 B/O2 radical initiation. After enantiomer separation (chiral stationary phase HPLC), aqueous conditions provoked aggregation. Detailed structural evolution was afforded by ECD/CPL monitoring. Three regimes can be observed and characterized by strong modifications in chiroptical patterns under, at, or above a 70 % H2 O : THF threshold. In luminescence, high glum dissymmetry factors values were obtained, up to 0.022, as well as a double sign inversion of CPL signals during the aggregation, a behavior rationalized by time-dependent density functional theory (TDDFT) calculations. Langmuir layers of enantiopure disulfide macrocycles were formed at the air-water interface and transferred onto solid substrates to afford Langmuir-Blodgett films, which were then studied by AFM and UV/ECD/fluorescence/CPL.

Strong Chiroptical Effects in the Absorption and Emission of Macrocycles Based on the 2,5-Diaminoterephthalate Minimal Fluorophore.

Chiral fluorescent macrocycles consisting of two to four units of dimethyl 2,5-diaminoterephthalate can be readily synthesized in a one-pot manner from inexpensive building blocks. Depending on the concentration, either a paracyclophane-like dimer with closely stacked benzene rings or a triangular trimer is the main product of the reaction. The macrocycles exhibit fluorescence in solution as well as in the solid state with maxima that are red-shifted with decreasing size of the macrocyclic ring and are observed at wavelengths from 590 (tetramer in solution) to 700 nm (dimer in the solid state). Chirality dictates the differential absorption and emission of circularly polarized light by these molecules. The ECD and CPL effects are particularly strong for the trimer, which is characterized by relatively large dissymmetry factors gabs =±2.8×10-3 at 531 nm and glum =±2.3×10-3 at 580 nm in n-hexane, being at the same time highly luminescent (Φfl =13.7 %). Despite the small chromophore, the circularly polarized brightness BCPL of 2.3 dm3 mol-1 cm-1 is comparable to values reported for other classes of established CPL emitters in the visible region, such as expanded helicenes or larger π-conjugated systems.

Ethylidene-Tethered Chromene-Pyrone Hybrids as Potential Plant-Growth Regulators from an Endolichenic Phaeosphaeria Species.

Phaeosphaeria sp., a lichen-associated fungus, produced six skeletally new dimeric spiciferones (1-6) and four known metabolites (7-10). The new structures were elucidated by spectroscopic analysis, and their absolute configurations were determined by electronic circular dichroism calculations. Compounds 1 and 3-6 represent the first examples of ethylidene-bridged dimers from the building blocks 4H-chromene-4,7(8H)-dione and α-pyrone, and 2 is a unique homodimer of spiciferone. Compounds 1, 2, and 5-9 significantly inhibited the growth of weed-like dicot Arabidopsis thaliana at 100.0 µM. Notably, 8 showed the strongest inhibitory activity against the fresh weight and root elongation of A. thaliana with the IC50 values of 32.04 and 26.78 µM, respectively, whereas 1, 8, and 9 stimulated the growth of A. thaliana at lower concentrations. Meanwhile, compounds 2 and 6 exhibited weak inhibitory effects on the root elongation of monocot rice, while 1 and 8 exhibited growth-promoting effects on the shoot and root elongation of rice in a roughly dose-dependent manner.

Chiral Diketopyrrolo[3,4-c]pyrrole-1,2,3-1H-triazole Dyes with Highly Tuneable Properties in Solution and Thin Films.

We have studied the impact of achiral substituents on the chiral supramolecular architectures of diketopyrrolo[3,4-c]pyrrole-1,2,3-1H-triazole (DPP) dyes. We decorated the same chiral DPP motif with substituent groups on the nitrogen atoms of the lactam moiety: the hydrophobic n-octyl alkyl chain, the hydrophilic tri(ethylene glycol) (TEG) chain and the thermo-cleavable tert-butoxycarbonyl (t-Boc) carbamate group. In spite of having identical conjugated chromophore and chiral appendages, in aggregated form the three dyes displayed profoundly different optical, chiroptical, electrochemical and thermal features. ECD measurements revealed differences in the aggregation modes, which would be inaccessible by most other techniques. We found strong chiroptical features, which would have major implications in the context of chiral organic opto-electronics and in the development of other highly innovative technological applications.

Synthesis and Stereodynamic and Emission Properties of Dissymmetric Bis-Aryl Carbazole Boranes and Identification of a CPL-Active B-C Atropisomeric Compound.

We synthesized bis-aryl carbazole borane derivatives having emissive properties and axial chirality. The resolution of a thermally stable atropisomeric pair (compound 1b), due to a B-C chiral axis, was achieved by chiral stationary-phase high-performance liquid chromatography (CSP-HPLC). Complete photophysical properties of all compounds were measured and simulated by time-dependent density functional theory (TD-DFT) calculations of the complete fluorescence cycle, and circularly polarized luminescence spectra were obtained for the atropisomers of compound 1b, whose absolute configuration was derived using a TD-DFT simulation of the electronic circular dichroism (ECD) spectra.

Atypical Angucyclinones with Ring Expansion and Cleavage from a Marine Streptomyces sp.

A unique ring C-expanded angucyclinone, oxemycin A (1), and seven new ring-cleavage derivatives (2-5 and 9-11) were isolated from the marine actinomycete Streptomyces pratensis KCB-132, together with eight known analogues (6-8 and 12-16). Their structures were elucidated by spectroscopic analyses, single-crystal X-ray diffractions, and NMR and ECD calculations. Among these atypical angucyclinones, compound 1 represented the first seven-membered ketoester in the angucyclinone family, which sheds light on the origin of fragmented angucyclinones with C-ring cleavage at C-12/C-12a in the Baeyer-Villiger hypothesis, such as 2-4, while the related "nonoxidized" analogues 5-8 seem to originate from a diverse pathway within the Grob fragmentation hypothesis. Additionally, we have succeeded in the challenging separation of elmenols E and F (12) into their four stereoisomers, which remained stable in aprotic solvents but rapidly racemized under protic conditions. Furthermore, the absolute configurations of LS1924 and its isomers (14 and 15) were assigned by ECD calculations for the first time. Surprisingly, these two bicyclic acetals are susceptible to hydrolysis in solution, resulting in fragmented derivatives 17 and 18 with C-ring cleavage between C-6a and C-7. Compared with ring C-modified angucyclinones, ring A-cleaved 11 was more active to multiple resistant "ESKAPE" pathogens with MIC values ranging from 4.7 to 37.5 µg/mL.

A Unique and Stable Polyproline I Helix Sorted out from Conformational Equilibrium by Solvent Polarity.

Polyproline I helical structures are often considered as the hidden face of their most famous geminal sibling, Polyproline II, as PPI is generally spotted only within a conformational equilibrium. We designed and synthesized a stable Polyproline I structure exploiting the striking tendency of (S)-indoline-2-carboxylic acid to drive the peptide bond conformation toward the cis amide isomer, when dissolved in polar solvents. The cooperative effect of only four amino acidic units is sufficient to form a preferential structure in solution. We shed light on this rare secondary structure with a thorough analysis of the spectroscopic and chiroptical properties of the tetramer, supported by X-ray crystallography and computational studies.