Electronic Structures of Pt(0) Complexes and Atomically Precise Clusters from Solid-State ¹⁹⁵Pt NMR Signatures.

Area of Science:

• Inorganic Chemistry
• Materials Science
• Spectroscopy

Background:

• Metal clusters exhibit unique properties valuable for diverse applications and fundamental studies of metal systems.
• Previous research focused on theoretical rationalization of cluster structures, lacking experimental spectroscopic validation.
• Relating theoretical models to specific spectroscopic signatures of metal clusters remains an underexplored area.

Purpose of the Study:

• To establish solid-state NMR as a tool for distinguishing metal sites in platinum clusters.
• To experimentally validate computational molecular orbital (MO) diagrams using NMR data.
• To apply this approach to known and novel platinum cluster structures.

Main Methods:

• Studied a series of platinum (Pt) clusters (Pt_n(0)) with varying nuclearities.
• Utilized ¹⁹⁵Pt solid-state Nuclear Magnetic Resonance (NMR) spectroscopy.
• Performed computational analysis of molecular orbital (MO) diagrams for the studied clusters.

Main Results:

• ¹⁹⁵Pt NMR effectively differentiates metal sites within platinum clusters.
• NMR spectral analysis provides experimental validation for computed MO diagrams.
• The approach was successfully applied to known platinum phosphine/carbonyl clusters and a novel Pt₅ cluster.

Conclusions:

• Solid-state NMR is a versatile method for characterizing metal sites in clusters.
• This NMR-based approach bridges theoretical calculations and experimental spectroscopy.
• The methodology is extendable to other metal clusters and nanostructures with NMR-active centers.