Achieving large thermal hysteresis in an anthracene-based manganese(II) complex via photo-induced electron transfer.

Abstract

Achieving magnetic bistability with large thermal hysteresis is still a formidable challenge in material science. Here we synthesize a series of isostructural chain complexes using 9,10-anthracene dicarboxylic acid as a photoactive component. The electron transfer photochromic Mn²⁺ and Zn²⁺ compounds with photogenerated diradicals are confirmed by structures, optical spectra, magnetic analyses, and density functional theory calculations. For the Mn²⁺ analog, light irradiation changes the spin topology from a single Mn²⁺ ion to a radical-Mn²⁺ single chain, further inducing magnetic bistability with a remarkably wide thermal hysteresis of 177 K. Structural analysis of light irradiated crystals at 300 and 50 K reveals that the rotation of the anthracene rings changes the Mn1-O2-C8 angle and coordination geometries of the Mn²⁺ center, resulting in magnetic bistability with this wide thermal hysteresis. This work provides a strategy for constructing molecular magnets with large thermal hysteresis via electron transfer photochromism.