Interlayer and intralayer magnetic interactions for room-temperature strong ferrimagnetism of layered organic–inorganic hybrid nanoplates

In the past few decades, a development of organic magnets with room-temperature strong ferromagnetism is challenged by the difficulty of creating three-dimensional (3D) long-range magnetic orderings in organic materials at a temperature higher than room temperature. Here, we report room-temperature ferrimagnetism of a tetragonal organic–inorganic hybrid Fe14Se16(tepa)III (tepa = tetraethylenepentamine), where III represents a coordination of a tepa molecule with a Fe3+ ion for an organic complex. The layered hybrid in a nanoplate-like shape is formed by periodic incorporation of tetragonal β-Fe3Se4 inorganic layers and organic spacing layers consisting of tepa and Fe3+. Fe14Se16(tepa)III shows a saturation magnetization MS of 7.2 emu g−1 at 300 K and a record-high Néel temperature TN (>560 K) in the organic magnets reported experimentally. A Mössbauer spectrum confirms a 3D long-range magnetic ordering of Fe2+ [S = 2 (71.4%)] and Fe3+ ions [S = 5/2 (21.7%) and 1/2 (4.0%)] in β-Fe3Se4 layers and organic spacing layers of Fe14Se16(tepa)III,9. First-principles calculations explain that the 3D long-range antiferromagnetic interactions between interlayer and intralayer irons result in the strong ferrimagnetism of Fe14Se16(tepa)III. This study unveils the possibility of tuning magnetic couplings of interlayer and intralayer high-spin Fe3+ and Fe2+ for enhancing the ferrimagnetism of layered hybrids and, thus, for future room-temperature magnetic/spintronic applications.