105 K Wide Room Temperature Spin Transition Memory Due to a Supramolecular Latch Mechanism

Little is known about the mechanisms behind the bistability (memory) of molecular spin transition compounds over broad temperature ranges (>100 K). To address this point, we report on a new discrete Fe-II neutral complex [(FeL2)-L-II](0) (1) based on a novel asymmetric tridentate ligand 2-(5-(3-methoxy-4H-1,2,4-triazol-3-yl)-6-(1H-pyrazol-1-yl))pyridine (L). Due to the asymmetric cone-shaped form, in the lattice, the formed complex molecules stack into a one-dimensional (1D) supramolecular chain. In the case of the rectangular supramolecular arrangement of chains in methanolates 1-A and 1-B (both orthorhombic, Pbcn) differing, respectively, by bent and extended spatial conformations of the 3-methoxy groups (3MeO), a moderate cooperativity is observed. In contrast, the hexagonal-like arrangement of supramolecular chains in polymorph 1-C (monoclinic, P2(1)/c) results in steric coupling of the transforming complex species with the peripheral flipping 3MeO group. The group acts as a supramolecular latch, locking the huge geometric distortion of complex 1 and in turn the trigonal distortion of the central Fe-II ion in the high-spin state, thereby keeping it from the transition to the low-spin state over a large thermal range. Analysis of the crystal packing of 1-C reveals significantly changing patterns of close intermolecular interactions on going between the phases substantiated by the energy framework analysis. The detected supramolecular mechanism leads to a record-setting robust 105 K wide hysteresis spanning the room temperature region and an atypically large T-LIESST relaxation value of 104 K of the photoexcited high-spin state. This work highlights a viable pathway toward a new generation of cleverly designed molecular memory materials.

Automated summary

This study reports a new type of neutral Fe-II complex based on a novel asymmetric ligand. The complex forms a one-dimensional supramolecular chain due to its asymmetric shape in the lattice. The different spatial conformations of the 3-methoxy groups in the supramolecular arrangement have different effects on the spin transition process of the compound. It was found that one of the supramolecular arrangements can keep the compound in a high-spin state over a large temperature range.