We performed a quantitative analysis of plasmon-assisted two-photon photochromic reactions on light-harvesting gold nanodimer structures. Our strategy for the quantitative analysis of two-photon-induced photochemical reactions on gold nanostructures is using not only a confined photochemical reaction chamber but also a solution system. The strong intensification of near-field light at the nanogap positions on gold nanodimer pairs promoted two-photon absorption by a closed-form diarylethene derivative, resulting in highly efficient photochromic conversion to the open-form structure.

Chlorocuprate(i) ionic liquids can be well-stabilized, low-cost, efficient and green non-mercury catalysts for hydrochlorination of acetylene.

While reduction reactions are ubiquitous in chemistry, it is very challenging to further reduce electron-rich compounds, especially the anionic ones. In this work, the reduction of 1,3-butadienyl dianion, the anionic conjugated olefin, has been realized by divalent rare-earth metal compounds (SmI2), resulting in the formation of novel 2-butene tetraanion bridged disamarium­(III) complexes. Density functional theory (DFT) analyses reveal two features: (i) the single electron transfer (SET) from 4f atomic orbitals (AOs) of each Sm center to the antibonding π*-orbitals of 1,3-butadienyl dianion is feasible and the new HOMO formed by the bonding interaction between Sm 5d orbitals (AOs) and the π*-orbitals of 1,3-butadienyl dianion can accept favorably 2e– from 4f AOs of Sm­(II); (ii) the 2-butene tetraanionic ligand serves as a unique 10e– donating system, in which 4e– act as two σ-donation bonding interactions while the rest 6e– as three π-donation bonding interactions. The disamarium­(III) complexes represent a unique class of the bridged bis-alkylidene rare-earth organometallic complexes. The ligand-based reductive reactivity of 2-butene tetraanion bridged disamarium­(III) complexes demonstrates that 2-butene tetraanionic ligand serves as a 3e– reductant toward cyclooctatetraene (COT) to provide doubly COT-supported disamarabutadiene complexes. The reaction of the disamarium­(III) complexes with Cp*Li produces the doubly Cp*-coordinated Sm­(III) complexes via salt metathesis. In addition, the reaction with Mo­(CO)6 affords the oxycyclopentadienyl dinuclear complex via CO insertion.