Charge-transfer interactions govern the trans influence and electron-induced bond activation in linear Au(i)...

Area of Science:

• Inorganic Chemistry
• Computational Chemistry
• Materials Science

Background:

• Linear gold(I) complexes (X-Au-L) serve as model systems for studying trans influence.
• These complexes are relevant to focused electron-beam-induced deposition (FEBID), a technique utilizing electron-induced precursor fragmentation.

Purpose of the Study:

• To develop a predictive framework for screening gold precursors for FEBID.
• To understand the electronic factors governing precursor fragmentation and stability.

Main Methods:

• Density Functional Theory (DFT) with Natural Bond Orbital (NBO) analysis.
• Energy Decomposition Analysis (EDA) and Natural Orbital for Chemical Valence (ETS-NOCV).
• Time-Dependent DFT (TD-DFT) for hole-electron analysis and electron-attachment thermodynamics.

Main Results:

• Orbital interactions and charge transfer, specifically σ(Au-X)→σ*(Au-L) delocalization and ligand lone-pair donation, govern Au-L bond strengthening and Au-X bond weakening.
• An electron-induced lability metric (G_lab) and a trigger proxy (Sr) were defined.
• A precursor viability index (PVI3) was constructed, combining G_lab and interaction stabilization (S_int) as benefits and Sr as a penalty.

Conclusions:

• ClAu(SMe2)2 and ClAu(SeMe2)2 are identified as the most promising precursors within the studied series.
• The developed PVI3 offers a reproducible framework for screening precursors for FEBID and similar electron-induced processes.