2[Mn(acacen)]+ + 1[Fe(CN)5NO]− polynuclear heterobimetallic coordination compounds of different dimensionality in the solid state

Abstract

Depending on the synthetic conditions, five heterometallic Mn^IIIFe^II polynuclear compounds with the same ratio of constituents, 2[Mn(acacen)]⁺/[Fe(CN)₅NO]²⁻, of different nuclearity and dimensionality (0D, 1D, 2D) were isolated. A [Mn(acacen)MeOH]₂[Fe(CN)₅NO]·1.5MeOH, 1 complex has been prepared by reaction of Mn^III/Schiff base (SB) complex, [Mn(acacen)Cl] (H₂acacen is N,N′-ethylenebis(acetylacetoneimine)) with sodium nitroprusside (NP). Single crystal X-ray diffraction analyses reveal that crystallization of 1 from coordinating or non-coordinating solvents results in different coordination polynuclear materials: from C₂H₅OH [{Mn(acacen)H₂O}₂Fe(CN)₅NO]·C₂H₅OH, 2, a trinuclear complex is formed; from CH₃CN [{Mn(acacen)H₂O}₄Fe(CN)₅NO][Fe(CN)₅NO]·4CH₃CN, an ionic compound with a pentanuclear bimetallic cation is formed 3; from i-C₃H₇OH [{Mn(acacen)}₂(i-PrOH)Fe(CN)₅NO]_n, a coordination chain polymer 4 is formed; from toluene [{Mn(acacen)}₂Fe(CN)₅NO]_n, a layered network 5 is formed. As the magnetic measurements show, for all compounds the weak interaction between Mn^IIIS = 2 spins through the NP bridge is antiferromagnetic and exhibits no significant photoactivity.