Two Antiferromagnetic Tetradecanuclear Iron Oxo Clusters Derived from a Pentadecanuclear Cluster via Substitutions of Shell Iron Polyhedra with Non-Metallic Oxoanions.

Substituting certain atoms in a metal-oxo cluster (MOC) can enrich its structure, properties, and applications, often involving the replacement of one metal polyhedron with another that exhibits a comparable coordination environment. Herein, we synthesized three clusters , , and , with the crystal compositions of [Fe(SO)O(tea)Cl](FeClOFeCl)·4(CHN)·18(HO) (tea = deprotonated triethanolamine), [Fe(SeO)O(tea)Cl](FeClOFeCl)·(CHN)·20(HO), and [FeO(tea)Cl](FeCl)·Cl·22(HO), using similar solvothermal methods. All three clusters exhibit similar cage-like structures, with (X = S or Se) differing by substituting a shell iron polyhedron with a nonmetallic XO tetrahedron.