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The substitution of fluorine atoms for oxygen atoms/hydroxyl groups has emerged as a promising strategy to enhance the physical and chemical properties of oxides/hydroxides in fluorine chemistry. However, distinguishing fluorine from oxygen/hydroxyl in the reaction products poses a significant challenge in existing characterization methods. In this study, we illustrate that terahertz (THz) spectroscopy provides a powerful tool for addressing this challenge. To this end, we investigated two fluorination reactions of boric acid, utilizing MHF2 (M=Na, C(NH2)3) as fluorine reagents. Through an interplay between THz spectroscopy and solid‐state density functional theory, we have conclusively demonstrated that fluorine atoms exclusively bind with the sp3‐boron but not with the sp2‐boron in the reaction products of Na[B(OH)3][B3O3F2(OH)2] (NaBOFH) and [C(NH2)3]2B3O3F4OH (GBF2). Based on this evidence, we have proposed a reaction pathway for the fluorinations under investigation, a process previously hindered due to structural ambiguity. This work represents a step forward in gaining a deeper understanding of the precise structures and reaction mechanisms involved in the fluorination of oxides/hydroxides, illuminated by the insights provided by THz spectroscopy. [ABSTRACT FROM AUTHOR]

The manganese tricarbonyl complex {[Mn2(CO)6Mn(H2O)4(BPDC)2]·2H2O}n (1) (BPDC = 2,2′-bipyridyl-4,4′-dicarboxylic acid) was synthesized from the reaction of MnBr(CO)5 with 2,2′-bipyridyl-4,4′-dicarboxylic acid. Various fac-Mn(CO)3 cores based on mononuclear complexes were achieved and only a handful of the Mn(I)-based dinuclear metallastirrups or supramolecular rectangles were reported. Interestingly, our compound is the first example of a CORM with 1-D ladder-like chain and Mn(I)/Mn(II) mixed valence state. Studies show that 1 can release CO under three different wavelengths of light (Green: λ = 520–530 nm; Blue: λ = 465–470 nm; UV: λ = 365–370 nm) and CO releasing rate can be adjusted by changing the wavelength of the irradiation light. Density functional theory (DFT) calculations were conducted to analyze the effect of metal-to-ligand charge transfer (MLCT) on CO releasing behaviors. Furthermore, cellular viability assay and anti-inflammatory activities showed that 1 possessed biological compatibility but no systemic cytotoxicity, and could prevent LPS-induced secretion of TNF-α and NO in RAW264.7 cells. The results suggest that 1 may provide a therapeutic approach for inflammation. [ABSTRACT FROM AUTHOR]