Magnetic Response Properties of Coinage Metal Macrocyles. Insights into the Induced Magnetic Field through the Analysis of [Cu5(Mes)5], [Ag4(Mes)4], and [Au5(Mes)5] (Mes = 2,4,6-Me3C6H2)

Abstract

The complexity of the magnetic response of coinage metal macrocycles supporting closed-shell d10–d10 interaction has been studied through the analysis of [Cu5(Mes)5], [Ag4(Mes)4], and [Au5(Mes)5] (Mes = 2,4,6-Me3C6H2) by means of relativistic DFT methods. Our effort relies on the description of the overall shielding tensor (δ) surrounding the molecular space in terms of its components (δij, i, j = x, y, z) by using chemical shift tensor maps to unravel the magnetic complexity of such molecular arrays. Additionally, the diamagnetic, paramagnetic, and spin–orbit contributions to the through the space chemical shift tensor are depicted for the first time in order to gain more insight into the variation of the magnetic response according to the atomic number (Z) of the metallic core involved. Our results show a strong axis-dependent (orientation-dependent) behavior of the coinage macrocycles indicating that the magneto-responsive properties increase according to Z with the core electrons mainly contributing t...