The Rh(III)-catalyzed C-H functionalization and subsequent intramolecular cyclization between azobenzenes and vinylene carbonate is described herein. Depending on the electronic property of azobenzenes, this transformation results in the formation of (2H)-indazoles or dihydrocinnolin-4-ones through the generation of ortho-alkylated azo-intermediates followed by decarboxylation. Surprisingly, vinylene carbonate acts as an acetaldehyde or acetyl surrogate to enable the [4 + 1] or [4 + 2] annulation reaction. This transformation is characterized by its mild reaction conditions, simplicity, and excellent functional group compatibility.A tandem system comprising in-line diazo compound synthesis and downstream consumption in a rhodium-catalyzed cyclopropanation reaction has been developed. Passing hydrazone through a silica column absorbed with Cu(OAc)2-H2O/N,N-dimethylaminopyridine oxidized the hydrazone to generate an aryldiazoacetate in flow. The crude aryldiazoacetate elutes from this column directly into a downstream cyclopropanation reaction, catalyzed by the chiral dirhodium tetracarboxylates, Rh2(R-p-Ph-TPCP)4 and Rh2(R-PTAD)4. This convenient flow to batch method was applied to the synthesis of a range of 1,2-diarylcyclopropane-1-carboxylates in high yields and with high levels of enantioselectivity.A novel tandem Ru-catalyzed [2+2+2] cycloaddition of arylenynes to dihydrobiphenylenes followed by halogen-radical ring opening has been developed for the construction of tub-shaped halogenated benzocyclooctatetraenes (bCOT's). Cross-couplings and Diels-Alder reactions of the brominated bCOT's allow the formation of the corresponding eight-membered ring-fused PAH's. The halogen-radical ring opening probably occurs via a selective formation of a bis-allyl radical at the 1,3-cyclohexadiene moiety, halogenation at the bridgehead carbon, and finally electrocyclic ring opening.The deep learning (DL) method sometimes suffers from poor transferability due to the wrong structure, i.e., basis functions used as the kernel for dimension elevation. Thus, for solving specific problems, a broad and robust set of basis functions should be elaborated. The choice of basis is similar to the procedure in variational principles in quantum physical chemistry applications. This work applies the associated Laguerre and the spherical harmonic for feature generation of molecules and atomic interactions, showing better performance in both the real-space and momenta-space and significantly enhancing the transferability and interpretability to unfamiliar elements and structures over the previous models. Moreover, with the symmetry manifested by the angular part from the spherical harmonics, both the energy and distribution of excited state orbitals can be calculated. Besides, the special functions can also be used in other applications such as image classification.A green and highly efficient one-pot method for α-diaryl-β-alkynol derivatives in water at room temperature was developed using the cocatalysis of a Lewis acid and meso-tetraphenylporphyrin iron(III) chloride (FeTPPCl). The unprecedented transformation was promoted by a modulation of the charge properties of propargylic carbocation chemistry and the use of an in situ-generated oxonium ylide as a matching nucleophile. The reaction was performed in water at room temperature with a highly step-economic manipulation in good to excellent yields and with a broad substrate scope. Water also acts as the third reactant for the one-pot transformation. Notably, the FeTPPCl catalyst can be directly reused four times with a slight discount in yields.A novel 1,2-difunctionalization of alkynones via an umpolung strategy for the synthesis of tetrasubstituted olefins has been developed. This procedure is realized by a formal C-C σ-bond cleavage reaction of cyclic α,α-dithioketones and subsequent deprotection. Notable features of this approach include excellent yields, mild reaction conditions, a broad substrate scope, and operational simplicity.In both its gaseous and condensed forms, carbon dioxide has an ever-increasing impact on Earth's chemistry and human life and activities. However, many aspects of its high-pressure phase diagram remain unclear. In this work, we present a complete structural characterization of carbon dioxide fluids under geological conditions using extensive ab initio molecular dynamics simulations throughout a wide pressure and temperature range, corresponding to Earth's lower mantle. We identify and describe four different disordered regimes, including two polymeric forms and two molecular ones, all within the geothermal conditions of the lower mantle. At pressures below 40 GPa, we find that the molecular liquid becomes very reactive above 2000 K the C-O double bond routinely breaks, resulting in small and transient chains composed of CO2 units and frequently leading to an exchange of oxygen atoms between molecules. At higher pressures, in addition to the polymeric fluid previously reported at 3000 K, we find a polymeric system with glass-like behavior at lower temperatures, suggesting a complex interplay between kinetics and stability.Tungsten displays high strength in extreme temperature and radiation environments and is considered a promising plasma facing material for fusion nuclear reactors. SCH66336 chemical structure Unlike other metals, it experiences substantial irradiation hardening, which limits service life and presents safety concerns. The origin of ultrahigh-irradiation hardening in tungsten cannot be well-explained by conventional strengthening theories. Here, we demonstrate that irradiation leads to near 3-fold increases in strength, while the usual defects that are generated only contribute less than one-third of the hardening. An analysis of the distribution of tagged atom-helium ions reveals that more than 87% of vacancies and helium atoms are unaccounted for. A large fraction of helium-vacancy complexes are frozen in the lattice due to high vacancy migration energies. Through a combination of in situ nanomechanical tests and atomistic calculations, we provide evidence that irradiation hardening mainly originates from high densities of atomic-scale hidden point-defect complexes.