Crystalline Divinyldiarsene Radical Cations and Dications

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Materials Science

Background:

• Divinyldiarsenes are precursors to arsenic-containing compounds.
• Understanding the electronic structure of arsenic species is crucial for developing new materials.

Purpose of the Study:

• To synthesize and characterize novel divinyldiarsene radical cations and dications.
• To investigate the structural and electronic changes upon sequential one-electron oxidation.
• To explore the properties of these arsenic compounds using spectroscopic and computational methods.

Main Methods:

• Synthesis of divinyldiarsene radical cations and dications using sequential oxidation with GaCl3.
• Characterization using X-ray diffraction, cyclic voltammetry, EPR/NMR spectroscopy, and UV/vis absorption spectroscopy.
• Theoretical analysis using Density Functional Theory (DFT) calculations.

Main Results:

• Readily accessible crystalline solids of divinyldiarsene radical cations [{(NHC)C(Ph)}As]2(GaCl4) and dications [{(NHC)C(Ph)}As]2(GaCl4)2 were obtained.
• Sequential oxidation led to predictable changes in bond lengths: elongation of the As=As bond and contraction of C-As bonds.
• UV/vis spectra showed strong visible absorptions, and EPR spectra revealed coupling with 75As nuclei.

Conclusions:

• The study successfully synthesized and characterized new arsenic radical cations and dications.
• Electronic and structural properties are tunable via sequential oxidation.
• These findings contribute to the understanding of arsenic bonding and reactivity.