Search Results (7)

Ground triplet 4,6-bis(trifluoromethyl)-1,3-phenylene bis(tert-butyl nitroxide) (TF2PBN) reacted with [Y(hfac)₃(H₂O)₂] (hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dionate), affording a doubly hydrogen-bonded adduct [Y(hfac)₃(H₂O)₂(TF2PBN)]. The biradical was recovered from the adduct through recrystallization. Crystallographic analysis indicates that the torsion angles (|θ| ≤ 90°) between the benzene ring and nitroxide groups were 74.9 and 84.8° in the adduct, which are larger than those of the starting material TF2PBN. Steric congestion due to o-trifluoromethyl groups gives rise to the reduction of π-conjugation. Two hydrogen bonds enhance this deformation. Susceptometry of the adduct indicates a ground singlet with 2J/k_B = −128(2) K, where 2J corresponds to the singlet–triplet gap. The observed magneto-structure relation is qualitatively consistent with Rajca’s pioneering work. A density functional theory calculation at the UB3LYP/6-311+G(2d,p) level using the atomic coordinates determined provided a result of 2J/k_B = −162.3 K for the adduct, whilst the corresponding calculation on intact TF2PBN provided +87.2 K. After a comparison among a few known compounds, the 2J vs. |θ| plot shows a negative slope with a critical torsion of 65(3)°. The ferro- and antiferromagnetic coupling contributions are balanced in TF2PBN, being responsible for ground-state interconversion by means of small structural perturbation like hydrogen bonds. Full article

β-γ-unsaturated spirolactones are easily available by Birch reduction. We describe their photochemistry in the presence of or without carbonyl compounds. The spirolactones show a distinct absorption band at 230 nm, which is not present in other cyclohexadienes. We explain this behavior by an interaction of the double bonds with the carbonyl group through space, further proven by TDDFT calculations. This allows their direct excitation with UV-C light. Interestingly, we obtain only products of an oxa-di-π-methane rearrangement, hitherto unknown for lactones. This speaks for a reaction pathway starting from singlet states, confirmed by calculated relative energies of biradical intermediates. Although polymerization is the main side reaction, we were able to isolate tricyclic lactones in moderate yields in a pure form. In the presence of benzaldehyde or benzophenone, excitation with UV-B light was possible, leading to H-atom abstraction in the allylic position and formation of alcohols. With an electron-rich double bond, the Paternó–Büchi products were isolated as well. The different diastereomers were separated by column chromatography or HPLC. Their relative configurations were determined using NOESY measurements or X-ray structure analysis. Overall, β-γ-unsaturated spirolactones show a remarkably different photochemistry compared to other cyclohexadienes, affording new products in only a few steps. Full article

Free radicals often interact with vital proteins, violating their structure and inhibiting their activity. In previous studies, synthesis, characterisation, and the antioxidative properties of the five different coumarin derivatives have been investigated. In the tests of potential toxicity, all compounds exhibited low toxicity with significant antioxidative potential at the same time. In this paper, the radical scavenging activity of the abovementioned coumarin derivatives towards ten different radical species was investigated. It was found that all investigated compounds show good radical scavenging ability, with results that are in correlation with the results published in the previous study. Three additional mechanisms of radical scavenging activity were investigated. It was found that all three mechanisms are thermodynamically plausible and in competition. Interestingly, it was found that products of the Double Hydrogen Atom Transfer (DHAT) mechanism, a biradical species in triplet spin state, are in some cases more stable than singlet spin state analogues. This unexpected trend can be explained by spin delocalisation over the hydrazide bridge and phenolic part of the molecule with a low probability of spin pairing. Besides radical-scavenging activity, the pharmacokinetic and drug-likeness of the coumarin hybrids were investigated. It was found that they exhibit good membrane and skin permeability and potential interactions with P-450 enzymes. Furthermore, it was found that investigated compounds satisfy all criteria of the drug-likeness tests, suggesting they possess a good preference for being used as potential drugs. Full article

It is our great pleasure to introduce the Festschrift of Chemistry to honor professor Josef Michl (Figure 1) on the occasion of his 80th birthday and to recognize his exceptional contributions to the fields of organic photochemistry, quantum chemistry, biradicals and biradicaloids, electronic and vibrational spectroscopy, magnetic circular dichroism, silicon and boron chemistry, supramolecular chemistry, singlet fission, and molecular machines [...] Full article

The α-methylated chalcones 7a–7e behave as P-type photochromic substances with photo-stationary states (PSS) as high as 15:85 when irradiated at 350 nm. These compounds are easily accessible in pure E-configuration by aldol condensation or by oxidative coupling/elimination. The α-methyl groups make these compounds potentially reactive with singlet oxygen following the gem-rule that predicts ¹O₂ regioselectivity. Even after long irradiations times in the presence of the singlet oxygen sensitizer tetraphenylporphyrin (TPP) and oxygen, however, no oxygenation products were detected. Under these conditions, all substrates were converted into 9:1 E/Z-mixtures despite the use of low-energy light that does not allow direct or sensitized excitation of the substrates 7. Additionally, chalcone 7a reduced the singlet oxygen reactivity of the tiglic ketone 3a by about a factor of two, indicating substantial physical quenching of singlet oxygen by the α-methylated chalcones 7a–7e. Thus, a singlet oxygen-induced E/Z-isomerization involving 1,2-dioxatetra-methylene biradicals that leads to triplet oxygen and thermodynamic E/Z-mixtures is postulated and supported by quantum chemical (DFT)-calculations. Full article

Octithiophene sterically segregated by annelation with bicyclo[2.2.2]octene (BCO) units was synthesized to study the unimolecular properties of longer oligothiophene dications. For the preparation of such longer oligomers, a new route for the synthesis of the monomer annelated with BCO unit at the 3,4-positions of thiophene ring was developed. Attempted synthesis of octithiophene 1(8T) fully annelated with BCO units was hampered by low solubility of the product, and octithiophene 2(8T) having octyl groups instead of the BCO units at the second rings from the both ends of 1(8T) was synthesized to solve the solubility problem. Neutral 2(8T) has a lower planarity due to the steric repulsion between the octyl substituents and the neighboring thiophene units. However, dication 2(8T)²⁺, which was obtained as a stable salt by chemical two-electron oxidation with NO⁺SbF₆^-, has a planar quinoid structure, as judged from a linear correlation between the inverse chain length and the absorption energy for 1(nT)²⁺ (n = 3,4,6) and 2(8T)²⁺. Based on the comparison with the calculated absorption spectra and the result of ESR inactive properties, 2(8T)²⁺ appears to have a singlet ground state with open-shell biradical character rather than a closed-shell singlet structure. Full article

Unrestricted density functional theory (UDFT) can be used for the description of open-shell singlet (OSS) biradicals provided a number of precautions are considered. Biradicals that require a two-determinantal wave function (e.g. OSS state of carbenes) cannot be described by UDFT for principal reasons. However, if the overlap between the open-shell orbitals is small (the single electrons are located at different atomic centers) errors become small and, then, the principal failure of UDFT in these cases is not apparent and may even be disguised by the fact that UDFT has the advantage of describing spin polarization better than any restricted open shell DFT method. In the case of OSS biradicals with two- or multiconfigurational character (but a onedeterminantal form of the leading configuration), reasonable results can be obtained by broken-symmetry (BS)-UDFT, however in each case this has to be checked. In no case is it reasonable to lower the symmetry of a molecule to get a suitable UDFT description. Hybrid functionals such as B3LYP perform better than pure DFT functionals in BS-UDFT calculations because the former reduce the self-interaction error of DFT exchange functionals, which mimics unspecified static electron correlation effects, so that the inclusion of specific static electron correlation effects via the form of the wavefunction becomes more effective. Full article