Formation of Coinage-Metal···Fullerene Adducts. Evaluation of the Interaction Nature between Triangular Coinage Metal Complexes (M₃ = Cu, Ag, and Au) and C₆₀ through Relativistic Density Functional Theory Calculations

Abstract

The recent formation of [M 3 (3, ) 2 Pz) 3 ]−C 60 cocrystals in a 4:1 ratio have shown the coinage metal complex's ability to bind fullerene, acting as buckycatchers. Here, we clarify the nature of such interaction accounting for the stabilization of the whole assembly via two models of different 4:1 and 1:1 ratios, within the framework of relativistic dispersion-corrected density functional theory. Our results exhibit a strong van der Waals character in the interaction, supported by the electrostatic character of the acidic-M 3 ring provided by coinage metals. This feature held constant throughout the coinage metal group, providing further guidance for explorative synthesis efforts seeking to increase the strength and versatility of the binding capabilities of coinage metal complexes, which is useful for predicting the rise of noncovalent interactions toward less symmetric fullerenes and endohedral metallofullerenes. In addition, the observed van der Waals character is retained in the hypothetical systems involving representative fullerene fragments, based on corannulene (C 20 H 10 ) and sumanene (C 21 H 12 ). These results highlight the versatility of trinuclear complexes which can adopt a convex distortion highly suitable for interacting with curved π-surfaces. Moreover, the nature and strength of the interaction do not significantly vary with the number of [M 3 ] complexes in the C 60 fullerene case, suggesting that the number of coinage-metal units involved in the adduct formation is related to the π-surface area available in the fullerene structure and the stoichiometry employed in the co-crystallization. Hence, we envisage the exploration of novel supramolecular arrays for the formation of structures featuring preorganized domains involving fullerenes and other appealing π-systems.

Reactivity and Stability of Metalloporphyrin Complex Formation: DFT and Experimental Study

“…Metalloporphyrins have many roles in a variety of fields including chemical, medical, biologic, and physic. The Interaction of porphyrin and ligand or metalloporphyrin with other compounds can be observed by Density Functional Theory (DFT) calculation approach [ 8 , 9 ].…”

Synergic effects between boron and nitrogen atoms in BN-codoped C59−nBNnfullerenes (n= 1–3) for metal-free reduction of greenhouse N2O gas

“…We also investigated the nature of the interactions in N 2 O and CO adducts of C 59− n BN n , which seems to be affected by the composition of fullerene. 74,75 The quantum theory of atoms in molecules (QTAIM) 76 was used here to investigate the nature of interactions between fullerenes and adsorbed N 2 O or CO molecules. QTAIM is based on topological analysis of electron density, which determines the nature of a chemical bond by analyzing electron density at a specific point between interacting atoms, known as the bond critical point (BCP).…”

Substituent Effects in π‐Hole Regium Bonding Interactions Between Au(p‐X‐Py)2Complexes and Lewis Bases: Anab initioStudy

“…[36] The terms regium bond (RgB) and coinage bond (CiB) have been used indistinctly in the literature to describe noncovalent interactions involving elements belonging group 11 (Cu, Ag and Au). [37,38] Both theoretical and experimental studies have been reported [39][40][41][42][43][44][45][46] that illustrate the ability of group 11 of elements to participate in σ-hole interactions. In addition, the interplay between RgBs and other noncovalent interactions has been also analyzed theoretically.…”