The electronic structure and magnetic interactions of three members of the breathing crystal Cu(hfac)2 LR family (hfac=hexafluoroacetylacetonato, LR =pyrazole-substituted nitronyl nitroxides with R=Me, Et, Pr, iPr, Bu ), mainly Cu(hfac)2 LPr (1), Cu(hfac)2 LBu ⋅0.5 C8 H18 (2) and Cu(hfac)2 LBu ⋅0.5 C8 H10 (3), have been analyzed by means of periodic plane-wave based DFT+U calculations. These CuII -nitroxide based molecular magnets display thermally and optically induced switchable behavior and light-induced excited spin state trapping phenomena. The calculations confirm the presence of temperature-dependent exchange interaction within the spin triads formed by the nitroxide-copper(II)-nitroxide units, in line with the changes observed in the effective magnetic moment. Moreover, they quantify the interchain interaction mediated by the terminal nitroxide group of two spin triads in neighboring polymer chains. This interaction competes with the exchange interaction within the spin triads at high temperature, and introduces 1D exchange channels that do not coincide with the polymeric chains. The density of states reveal that the low-lying conduction states potentially involved in the UV/Vis transitions are located on the nitroxide radicals, the hfac groups and the Cu atoms. Then, the density of states is almost independent of the solvent and the R group. This suggests the possibility of light-induced spin switching for other members of this family. The 500 nm band of the low-temperature phase can be ascribed to a ligand-to-metal charge transfer transition between the nitroxide and Cu bands.
Keywords: LIESST: spin crossover; density functional calculations; exchange interactions; light-induced spin transitions; switchable magnetic materials.
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