Unveiling Multilayered Metal Cation−π(Arene) Interactions in a Structurally Engineered Silver(III)-Corrole: Insights from Terahertz Spectroscopy

Metal
cation−π interactions, involving electrostatic
forces between a metal cation and an aromatic π-electron cloud,
play a critical role in molecular recognition, catalysis, and the
design of functional materials. In this work, we combined synthetic,
terahertz (THz) spectroscopic, and structural/computational study
to provide valuable insights into the nature and characterization
of these interactions in a tailor-made silver corrole complex, where
a 2-(3-(2-formylphenoxy)propoxy)phenyl group creates an appropriate
electronic environment around the silver(III) center for possible
metal cation−π(arene) interactions. The observed close
Ag···C distances in the crystal structure support the
metal cation−π interaction. Critically, THz spectroscopy
provided direct experimental evidence for the presence and nature
of these interactions, a finding further corroborated by computational
studies. To our knowledge, this represents the first application of
frequency-domain THz spectroscopy in demonstrating multilayered metal
cation−π interactions within such systems. The observed
η6-coordination of the silver ion to the aromatic
ring highlights its importance in structuring and stabilizing the
metal–ligand complex. These findings offer valuable information
for designing future molecular systems where metal cation−π
interactions are central to structure and stability, with implications
for catalysis and material science.