Single-Step Synthesis of An Ideal Chain Antiferromagnet [H2(4,4'-bipyridyl)](H3O)2Fe2F10 with Spin S = 5/2

Angew Chem Int Ed Engl. 2024 Sep 9:e202415700. doi: 10.1002/anie.202415700. Online ahead of print.

Abstract

One-dimensional (1D) magnets are of great interest owing to their intriguing quantum phenomena and potential application in quantum computing. We successfully synthesized an ideal antiferromagnetic spin S = 5/2 chain compound [H2(4,4'-bpy)](H3O)2Fe2F10 (4,4'-bpy = 4,4'-bipyridyl) 1, using a single-step low-temperature hydrothermal method under conditions that favors the protonation of the bulky bidentate ligand 4,4'-bpy. Compound 1 consists of well-separated (Fe3+-F-)¥ chains with a large Fe-F-Fe angle of 174.8°. Both magnetic susceptibility and specific heat measurements show that 1 does not undergo a magnetic long-range ordering down to 0.5 K, despite the strong Fe-F-Fe intrachain spin exchange J with J/kB = -16.2(1) K. This indicates a negligibly weak interchain spin exchange J'. The J'/J value estimated for 1 is extremely small (< 2.8×10-6), smaller than those reported for all other S = 5/2 chain magnets. Our hydrothermal synthesis incorporates both [H2(4,4'-bpy)]2+ and (H3O)+ cations into the crystal lattice with numerous hydrogen bonds, hence effectively separating the (Fe3+-F-)¥ spin chains. This single-step hydrothermal synthesis under conditions favoring the protonation of bulky bidentate ligands offers an effective synthetic strategy to prepare well-separated 1D spin chain systems of magnetic ions with various spin values.

Keywords: Antiferromagnetism; Hybrid Materials; Hydrothermal Synthesis; Spin chains; Spin liquid.