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

ABSTRACT: 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 [Fe^IIL₂]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, P2₁/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.

SUBMITTER: Seredyuk M 

PROVIDER: S-EPMC9380689 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature