Stable Ferromagnetic Crystal of Two‐Dimensional Manganese‐Chromium Oxalate with Supramolecular Cation

Abstract

A supramolecular cation of (m‐FAni+)(tst‐DCH[18]crown‐6), where m‐FAni+ and tst‐DCH[18]crown‐6 denote m‐fluoroanilinium and trans‐syn‐trans‐dicyclohexano[18]crown‐6, respectively, was introduced into a ferromagnetic {[MnIICrIII(oxalate)3]–} layer to obtain a stable organic‐inorganic hybridized crystal. The crystal structure of (m‐FAni+)(tst‐DCH[18]crown‐6){[MnIICrIII(oxalate)3]–} was constructed by alternate stacking of a two‐dimensional honeycomb layer of {[MnIICrIII(oxalate)3]–} and the supramolecular cations. Cyclohexyl moieties of tst‐DCH[18]crown‐6 penetrated the pores of the honeycomb layers, excluding solvent molecules in the crystal. The anionic layers showed ferromagnetic order of MnII and CrIII ions with S = 5/2 and S = 3/2 spins, respectively, at 5.5 K. Although the m‐FAni+ showed disorder with respect to 180° rotation of the aryl ring, no significant anomaly was observed in the dielectric response, suggesting that the disorder is static.

Solvent dependence of crystal structure and dielectric relaxation in ferromagnetic [MnCr(oxalate)3]− salt

“…For example, when trans-syn-trans-dicyclohexano [18]crown-6 exhibited a flat conformation, the cyclohexane incorporated into the crystal honeycomb holes prevented solvent incorporation. 24,25 In this study, we report a novel [MnCr(oxalate) 3 ] − -based hybrid crystal that maintains its crystalline state even after desolvation. The polar crystal (CBA + )( [18]crown-6)[MnCr (oxalate) 3 ] − (CH 3 OH) (1•CH 3 OH) (CBA + = 4-carboxybutan-1aminium) with space group Cc produced solvent-free crystals (CBA + )( [18]crown-6)[MnCr(oxalate) 3 ] − , 1, with space group C2 after heat treatment.…”

“…For example, when trans-syn-trans -dicyclohexano[18]crown-6 exhibited a flat conformation, the cyclohexane incorporated into the crystal honeycomb holes prevented solvent incorporation. 24,25…”