Unconventional mechanism and selectivity of the Pd-catalyzed C–H bond lactonization in aromatic carboxylic acid

The search for more effective and highly selective C–H bond oxidation of accessible hydrocarbons and biomolecules is a greatly attractive research mission. The elucidating of mechanism and controlling factors will, undoubtedly, help to broaden scope of these synthetic protocols, and enable discovery of more efficient, environmentally benign, and highly practical new C–H oxidation reactions. Here, we reveal the stepwise intramolecular SN2 nucleophilic substitution mechanism with the rate-limiting C–O bond formation step for the Pd(II)-catalyzed C(sp3)–H lactonization in aromatic 2,6-dimethylbenzoic acid. We show that for this reaction, the direct C–O reductive elimination from both Pd(II) and Pd(IV) (oxidized by O2 oxidant) intermediates is unfavorable. Critical factors controlling the outcome of this reaction are the presence of the η3-(π-benzylic)–Pd and K+–O(carboxylic) interactions. The controlling factors of the benzylic vs ortho site-selectivity of this reaction are the: (a) difference in the strains of the generated lactone rings; (b) difference in the strengths of the η3-(π-benzylic)–Pd and η2-(π-phenyl)–Pd interactions, and (c) more pronounced electrostatic interaction between the nucleophilic oxygen and K+ cation in the ortho-C–H activation transition state. The presented data indicate the utmost importance of base, substrate, and ligand in the selective C(sp3)–H bond lactonization in the presence of C(sp2)–H.

Modulating Room-Temperature Phosphorescence-To-Phosphorescence Mechanochromism by Halogen Exchange

Modulating the stimulus-responsiveness of a luminescent crystal is challenging owing to the complex interdependent nature of its controlling factors, such as molecular structure, molecular conformation, crystal packing, optical properties, and amorphization behavior. Herein, we demonstrate a halogen-exchange approach that disentangles this problem, thereby realizing the modulation of room-temperature phosphorescence-to-phosphorescence mechanochromism. Replacing the bromine atoms in a brominated thienyl diketone with chlorine atoms afforded isostructural crystals; i.e., molecules with different halogen atoms exhibited the same molecular conformation and crystal packing. Consequently, amorphization behavior toward mechanical stimulation was also the same, and the phosphorescence of amorphous states originated from the same conformer of each diketone. In contrast, the phosphorescence properties of each conformer were modulated differently, which is ascribable to heavy atom effects, resulting in the modulation of the mechanochromism. Thus, halogen exchange is a promising approach for modulating the stimulus-responsive photofunctions of crystals involving spin-forbidden processes.

Vertical Distribution and Controlling Factors of Soil Inorganic Carbon in Poplar Plantations of Coastal Eastern China

Afforestation is a strategy to protect croplands and to sequestrate carbon in coastal areas. In addition, inorganic carbon is a considerable constitute of the coastal soil carbon pool. However, the vertical distribution and controlling factors of soil inorganic carbon (SIC) in plantations of coastal areas have been rarely studied. We analyzed the SIC content as well as physiochemical properties along soil profiles (0–100 cm) in young (YP) and mature (MP) poplar plantations in coastal eastern China. The soil profile was divided into six layers (0–10, 11–20, 21–40, 41–60, 61–80 and 81–100 cm) and a total of 36 soil samples were formed. The SIC content first increased from 0–10 cm (0.74%) to 11–20 cm (0.92%) and then fluctuated in the YP. In contrast, the SIC content increased with increasing soil depth until 40 cm and then leveled off, and the minimum and maximum appeared at 0–10 cm (0.54%) and 81–100 cm (0.98%) respectively in the MP. The soil inorganic carbon density was 12.05 and 12.93 kg m−2 within 0–100 cm in the YP and MP, respectively. Contrary to SIC, soil organic carbon (SOC) first decreased then levelled off within the soil profiles. Compared with the YP, the SIC content decreased 27.8% at 0–10 cm but increased 13.2% at 21–40 cm, meanwhile the SOC content in MP decreased 70.6% and 46.7% at 21–40 cm and 61–80 cm, respectively. The water-soluble Ca2+ and Mg2+ gradually decreased and increased, respectively within the soil profiles. The soil water-soluble Ca2+ increased 18.3% within 41–100 cm; however, the soil water-soluble Mg2+ decreased 32.7% within 21–100 cm in the MP when compared to the YP. Correlation analysis showed that SIC was negatively correlated with SOC, but positively correlated with soil pH and water-soluble Mg2+. Furthermore, structural equation modeling (SEM) indicated that SOC was the most important factor influencing the SIC content in the studied poplar plantations, indicating SOC sequestration promoted the dissolution of SIC. Therefore, our study highlights the trade-off between SIC and SOC in poplar plantations of coastal Eastern China.