A Quest for Effective F NMR Spectra Modeling: What Brings a Good Balance Between Accuracy and Computational Cost in Fluorine Chemical Shift Calculations?

This work proposes a systematic study of different computational schemes for fluorine Nuclear Magnetic Resonance (F NMR) chemical shifts, with special emphasis placed on the basis set issue. This study encompasses two stages of calculation, namely, the development of the computational schemes for the geometry optimization of fluorine compounds and the NMR chemical shift calculations. In both stages, the performance of different density functional theory functionals is considered against the method of coupled-cluster singles and doubles (CCSD), with the latter representing a theoretical reference in this work.

Activation of Anthraquinone's Electrophilicity by Light for a Dynamic C-O Bond.

Coupling of photoswitching with dynamic covalent chemistry enables control of the formation and cleavage of covalent bonds by light irradiation. -Aryloxyanthraquinones feature an exclusive ability to switch electrophilicity by interconversion between - and -quinone isomers, which was used for the first time for the implementation of a dynamic C-O bond. Photogenerated -isomers undergo a concerted -Michael addition of phenols to give hitherto unknown 4-hydroxy-10,10-diaryloxyanthracen-9-ones.

Computational F NMR of trifluoromethyl derivatives of alkenes, pyrimidines, and indenes.

The F NMR chemical shifts of 13 trifluoromethyl derivatives of alkenes, pyrimidines, and indenes were calculated at the DFT level using the BhandHLYP, BHandH, PBE, PBE0, O3LYP, B3LYP, KT2, and KT3 functionals in combination with the pcS-2 basis set. Best result was documented for the BHandHLYP functional: The mean absolute error (MAE) of 0.66 ppm for the scaled values was achieved for the range of about 20 ppm.

Fluorine spin-spin coupling constants of pentafluorobenzene revisited at the ab initio correlated levels.

All possible spin-spin coupling constants, F- F, F- C, and F- H, of pentafluorobenzene were calculated at five different levels of theory, HF, DFT, SOPPA (CCSD), CCSD, and the SOPPA (CCSD)-based composite scheme with taking into account solvent, vibrational, relativistic, and correlation corrections. Most corrections were next to negligible for the long-range couplings but quite essential for the one-bond carbon-fluorine coupling constants. Hartree-Fock calculations were found to be entirely unreliable, while DFT results were comparable in accuracy with the data obtained using the wave function-based methods.

Stereochemical dependence of substituent γ-effects in the F NMR shielding constants.

The substituent α-, β-, and γ-effects of the elements of the second and third periods on F NMR chemical shifts are evaluated including the establishment of stereochemical dependence of γ-effect, the latter particularly important in stereochemical studies of fluorine-containing compounds. Benchmark calculations performed for a series of 32 simple inorganic fluorine-containing molecules demonstrated a markedly good correlation between calculated and experimental fluorine chemical shifts characterized by a mean absolute error of 22.5 ppm in the range of about 900 ppm, which corresponds to a 2.