Ag(III)···Ag(III) Argentophilic Interaction in a Cofacial Corrole Dyad

Abstract

Metallophilic interactions between closed-shell metal centers are exemplified by d10 ions, with Au(I) aurophilic interactions as the archetype. Such an interaction extends to d8 species, and examples involving Au(III) are prevalent. Conversely, Ag(III) argentophilic interactions are uncommon. Here, we identify argentophilic interactions in silver corroles, which are authentic Ag(III) species. The crystal structure of a monomeric silver corrole is a dimer in the solid state, and the macrocycle exhibits an atypical domed conformation. In order to evaluate whether this represents an authentic metallophilic interaction or a crystal-packing artifact, the analogous cofacial or “pacman” corrole was prepared. The conformation of the monomer was recapitulated in the silver pacman corrole, exhibiting a short 3.67 Å distance between metal centers and a significant compression of the xanthene backbone. Theoretical calculations support the presence of a rare Ag(III)···Ag(III) argentophilic interaction in the pacman complex.

Where are the Excess Electrons in Subvalent Compounds? The Case of Ag7Pt2O7

“…Subvalence has been usually discussed in the playground of orbital overlap and d 10 -d 10 closed shell interactions. ,, A suitable framework to quantify the energies associated with these interactions is the COHP analysis . It allows a partition of the band structure energy that provides an accurate estimation of the orbital interaction energies between atoms pairs.…”

“…Subvalent compounds defy traditional chemical bonding rules involving conventional oxidation states since their atoms contribute to the bonding network with fewer valence electrons than expected from their electronic configuration. In the family of silver compounds, the anomalous composition inherent to subvalence also opens the door to new chemistry, , where metallophilic interactions , change the conventional chemical view due to the participation of closed-shell d 10 orbitals in spd hybridization. − Thanks to the interplay between metallic and ionic bonding, subvalent compounds can be considered “for the design of next-generation multifunctional materials”, with specific applications in the energy storage field. , However, a general framework able to unveil structure–property relationships has not yet been established and becomes necessary to advance the understanding of these subvalent materials.…”

Magnetic Circular Dichroism of Porphyrinoid Silver Complexes: Evidence of the Electronic Structure Inversion upon Protonation of the N-Confused Core

“…Silver porphyrins have been known for decades since the initial report of the EPR spectrum of silver deuteroporphyrin IX dimethyl ester in 1961 . One of the unique features of these systems is the accessibility of both Ag­(II) and Ag­(III) oxidation states in which the silver ion remains in the square-planar porphyrin coordination environment. − Since their discovery, silver porphyrins have been investigated, e.g., for electrocatalytic and biomedical applications. − The silver complexes of porphyrin isomers and analogues, such as N-confused porphyrins, − core-modified porphyrins, , and corroles, − have received significantly less attention. − …”