Electronic Structure and Magnetic Behavior in Polynuclear Transition‐Metal Compounds

Deciphering the origin of million-fold reactivity observed for the open core diiron [HO–FeIII–O–FeIVO]2+species towards C–H bond activation: role of spin-states, spin-coupling, and spin-cooperation

“…1d ) also suggesting a valence localisation of the spins. The magnetic coupling of the complex 1 for a high spin ( S = 2 and S = 5/2) is computed using the ground state structure employing the standard protocol, 145 and this gives a J value of –137.3 cm –1 , and this matches well with the experimental estimate of –90 ± 20 cm –1 reported using EPR studies 73 offering confidence in the estimated structures and properties. Here, we have computed the overlap integral between two SOMOs of the Fe centres 108 and a significant overlap is noted between the SOMOs of d yz and d xz orbitals of Fe III and Fe IV centres, respectively, and this strong overlap is found to be responsible for the strong antiferromagnetic coupling observed (see Tables S6 and S7 in the ESI † ).…”

Synthesis, Structural Features and Physical Properties of a Family of Triply Bridged Dinuclear 3d-4f Complexes

“…Calculations were performed on complexes 1 and 6 derived from experimental crystallographic geometries. The approach used to determine the exchange coupling constants for polynuclear complexes has been described in detail elsewhere [65][66][67][68].…”

Nickel(II) salicylaldiminates: Re-visiting a classic

“…Calculations based on Density Functional Theory provide an excellent estimation of the exchange coupling constants in polynuclear transition metal complexes despite the very small energy differences involved. 26,27 Detailed description of the computational procedure employed to calculate the exchange coupling constants in polynuclear complexes has been previously provided by some of us. 28,29 The calculations were performed using Gaussian16 B.01 version 30 with the B3LYP functional 31 and an all electron basis set (Def2TZV).…”