Mechanistic insights into copper-mediated benzylic C(sp)-H bond trifluoromethylation.

The mechanisms underlying copper-mediated trifluoromethylation of benzylic C(sp)-H bonds were investigated using density functional theory (DFT) calculations. Two distinct pathways were identified: radical recombination/reductive elimination and single-electron transfer (SET). In the radical recombination/reductive elimination pathway, the Cu species recombines with benzyl radicals to generate a Cu intermediate, which subsequently undergoes reductive elimination.

Towards high-performance nonlinear optical materials through embedding a D-A system into β-ketoenamine-linked COFs.

Two covalent organic framework (COF) films supported by a glass substrate were obtained by solvothermal reaction of an electron donor with electron acceptor 1,3,5-triformylbenzene (TF) or 2,4,6-triformylphloroglucinol (TFP), respectively. The TFP-BD film exhibits a nonlinear absorption coefficient of -3.01 × 10 cm GW.

Deep transfer learning for predicting frontier orbital energies of organic materials using small data and its application to porphyrin photocatalysts.

Machine learning (ML) models have received increasing attention as a new approach for the virtual screening of organic materials. Although some ML models trained on large databases have achieved high prediction accuracy, the application of ML to certain types of organic materials is limited by the small amount of available data. On the other hand, metalloporphyrins and porphyrins (MpPs) have received increasing attention as potential photocatalysts, and recent studies have found that both HOMO/LUMO energy levels and energy gaps are important factors controlling the MpP photocatalysts.

Computational Exploration of Dirhodium Complex-Catalyzed Selective Intermolecular Amination of Tertiary vs. Benzylic C-H Bonds.

The mechanism and origins of site-selectivity of Rh(-tfpttl)-catalyzed C()-H bond aminations were studied using density functional theory (DFT) calculations. The synergistic combination of the dirhodium complex Rh(-tfpttl) with -butylphenol sulfamate TBPhsNH composes a pocket that can access both tertiary and benzylic C-H bonds. The nonactivated tertiary C-H bond was selectively aminated in the presence of an electronically activated benzylic C-H bond.