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UV-vis absorption and magnetic circular dichroism (MCD) spectra of octakis thioethyl "free base" porphyrazine H2OESPz and its metal complexes MOESPz (M = Mg, Zn, Ni, Pd, Cu), as well as of [MnOESPz(SH)] were recorded. In the last case, MCD proved to have quite good sensitivity to the coordination of this complex with 1-methylimidazole (1-mim) in benzene. Time-dependent density functional theory (TDDFT) calculations were carried out for the considered porphyrazine complexes and showed good performance on comparing with MCD and UV-vis experimental spectra, even in the open-shell Cu and Mn cases. Calculations accounted for the red shift observed in the thioalkyl compounds and allowed us to reveal the role of sulfur atoms in spectroscopically relevant molecular orbitals and to highlight the importance of the conformations of the thioethyl external groups. Calculated MCD spectra of [MnOESPz(SH)] confirm the Mn(III) → Mn(II) redox process, which leads to the [Mn(OESPz)(1-mim)2] species, and the relevance of the spin state for MCD is revealed.

Vibrational circular dichroism (CD) and IR spectra of dichloromethane solutions of l-stercobilin and d-urobilin hydrochlorides have been recorded in the mid-IR region. The spectra are best interpreted by combining molecular dynamics calculations and density functional theory (DFT) calculations within the quantum mechanics/molecular mechanics ONIOM-type framework, and the combined predicted results are better and more informative than the more standard analysis provided by DFT calculations. The same approach also sheds light on the Cotton effect sign inversion of room temperature versus low-temperature electronic CD spectra of the same compounds in methanol-glycerol solution. Finally, circularly polarized luminescence spectra for l-stercobilin in chloroform solution provide information on the excited-state geometry of this molecule.

Vibrational and electronic circular dichroism (VCD and ECD) spectra of 3 optically active bilirubin analogs with propionic acid groups replaced by (1) 1-(S)-methylpropyl groups, (2) 3-acetoxy-1-(S)-methylpropyl groups, and (3) 1-(S)-2-(R)-dimethyl-2-(methoxycarbonyl)ethyl groups have been recorded at different concentrations in chloroform. The aliphatic chains attached to C-8 and C-12 of the 3 chosen mesobilirubins were modified so as to possess no OH group. The variation of the VCD spectra with concentration is consistent with the formation of dimers at high concentration. Density functional theory and time-dependent density functional theory calculations on monomeric and dimeric forms support such a conclusion. Comparing with previous VCD (ECD) and IR (UV) studies of other mesobilirubin molecules, it is concluded that here, the key feature for aggregation is the missing OH groups on the propionic acid chains. The latter, in synergy with the polar groups of lactam moieties, appear to be involved in intramolecular phenomena and thus favor monomeric forms. Investigation of ECD and UV spectra of the same compounds in mixed DMSO/chloroform solutions provide further clues to the proposed picture.

The enantiomers of four chiral 3-aryl-substituted-γ-butyrolactones, key intermediates for the preparation of compounds of pharmaceutical interest, were successfully isolated by enantioselective chromatography, employing the Chiralpak AD-H chiral stationary phase. For all compounds the same elution order was observed, as monitored by a full set of chiroptical methods that we employed, namely ORD (optical rotatory dispersion), ECD (electronic circular dichroism, or CD in the UV range), and VCD (vibrational circular dichroism, or CD in the IR range). By density functional theory (DFT) calculations we were able to determine that the first eluted enantiomer has (S) absolute configuration in all four cases. We were able to justify the elution order by molecular docking calculations for all four enantiomeric pairs and suitable modeling of the stationary and mobile phases of the employed columns. The optimal performance of the chiroptical spectroscopies and of the DFT calculations allows us to formulate a lactone chirality rule out of the CO stretching region of the VCD spectra.

Raman and Raman optical activity (ROA), IR, and vibrational circular dichroism (VCD) spectra of (R)- and (S)-pantolactone have been recorded in three solvents. ROA has been employed on water and DMSO solutions, VCD on DMSO and CCl4 solutions. In the last solvent, monomer-dimer equilibrium is present. Due to the low conformational flexibility of the isolated molecule and to the possibility of aggregation, this compound has been used here to test different protocols for computation of the spectroscopic responses taking into account solvent effects. Molecular dynamics (MD) simulations have been carried out together with statistical clustering methods based on collective variables to extract the structures needed to calculate the spectra. Quantum mechanical DFT calculations based on PCM are compared with approaches based on different representations of the solvent shell (MM or QM level). Appropriate treatment of the solvent permits obtaining of good band-shapes, with the added advantage that the MD analysis allows one to take into account flexibility of dimeric structures justifying the broadness of observed bands and the absence of intense VCD couplets in the carbonyl and OH stretching regions.

The magnetic circular dichroism (MCD) spectra of metal complexes of tetrakis(thiadiazole)porphyrazines ([TTDPzM] with M = 2HI , ZnII , MgII (H2 O), and CdII ) have been recorded in dimethyl formamide solution. Together with the UV-Vis spectra, the MCD spectra provide useful information about the structure and electronic properties of the complexes. The experimental UV-Vis and MCD spectra compare pretty well with DFT calculations of two sorts, based either on the sum-over-states (SOS) approach or on the complex polarization propagator approach. They further corroborate the findings and interpretation of MCD spectra of porphyrazines based on the model of Michl for peripheral molecular orbitals. Magnetic circularly polarized luminescence (MCPL) spectra, quite uncommon in the literature, have been recorded for [TTDPzM] (M = 2HI , ZnII , MgII (H2 O)).

A computational expression for the Faraday A term of magnetic circular dichroism (MCD) is derived within coupled cluster response theory and alternative computational expressions for the B term are discussed. Moreover, an approach to compute the (temperature-independent) MCD ellipticity in the context of coupled cluster damped response is presented, and its equivalence with the stick-spectrum approach in the limit of infinite lifetimes is demonstrated. The damped response approach has advantages for molecular systems or spectral ranges with a high density of states. Illustrative results are reported at the coupled cluster singles and doubles level and compared to time-dependent density functional theory results., Submitted to J. Chem. Phys. on May 10, 2020

The conformational properties of natural bilirubin, bisbutyricmesobilirubin-XIIIα, and their chiral derivatives (βS,β′S)-dimethylmesobilirubin-XIIIα and 8,12-(γR,γ′R)- dimethylbisbutyricmesobilirubin-XIIIα were investigated by metadynamics, an improved molecular dynamics computational methodology useful for conformational analysis. Applied to linear tetrapyrroles, which may be treated as two blade molecular propellers, our results are represented by conformational energy hypersurface maps built as functions of the two central dihedral torsion angles (φ1 and φ2) following rotations of two dipyrrinone units about the connecting CH2, and are compared successfully with maps previously obtained from molecular mechanics. With an emphasis on the conformationally more flexible 8,12-(γR,γ′R)-dimethylbisbutyricmesobilirubin-XIIIα, a conformationally mobile optically active bilirubinoid with butyric acid replacing propionic, metadynamics reveals global and nearby minima. Its electronic circular dichroism and UV–Vis spectra predicted by DFT calculations correlate well with the experimental spectra and are explained on the basis of equilibrium between the predicted conformational energy minima.