Tuning the Spin Coupling Interactions in the Nitroxide-Based Bisphenol-Like Diradicals.

Abstract

The intramolecular spin coupling interactions of bisphenol-like trinary-bridged diradicals [nitroxide-(para/meta)phenylene-X-phenylene(para/meta)-nitroxide, X=C=CH2 , O, BH, NH and SO2 ] were explored with an emphasis on the tuning role of the X coupler at the (U)B3LYP/6-311++G(d,p) level. Our results indicate that all designed trinary-bridged diradicals featuring a V-type structure with a bending angle of 104-130° and torsional angles of two phenylene rings being 20-90° exhibit different diradical character and magnetism, depending on the structures and properties of the X bridges. More interestingly, although meta/para-phenylene supports a ferromagnetic (FM)/antiferromagnetic (AFM) coupling, their combinations by using X as a trinary bridge can mediate spin coupling, but the coupling magnitude strongly depends on X. In general, a para/para or meta/meta combination with X leads to an open-shell singlet ground state and thus AFM, but the meta/meta combination considerably decreases the spin coupling interaction. In contrast, a para/meta combination with X produces a triplet ground state and FM. Their combination with a single-electron conjugation end coupler (C=CH2 ) leads to an inverse coupling regularity. All results can be reasonably explained by the spin alternation rule, molecular structures, and properties. In particular, detailed spin coupling mechanisms are suggested to involve cooperative through-space and through-bond pathways with different levels of cooperativity. This is rationalized with the X-induced bending of the diradicals not only modifying the through-bond (extended π conjugation) pathway but also provididng a through-space (face-to-face vs. side-to-side π-π interaction) possibility for spin coupling, in conjunction with twisting of the phenylene rings. Different contributions of the through-space and through-bond couplings are quantitatively distinguished and depend on the structure and property of the X coupler. Clearly, this work reports interesting aspects of the trinary bridged diradicals and also provides important information for the design of molecules for functional magnetic materials and tuning their magnetic properties.