Various Structural Types of Cyanide-Bridged Fe(III)–Mn(III) Bimetallic Coordination Polymers (CPs) and Polynuclear Clusters Based-on A New mer-Tricyanoiron(III)Building Block: Synthesis, Crystal Structures, and Magnetic Properties

Four cyanide-bridged Fe(III)–Mn(III) complexes {[Fe(qxcq)(CN)(3)][Mn(L(1))(H(2)O)]}[Mn(L(1))(H(2)O)(CH(3)OH)](ClO(4))·1.5MeOH·0.5H(2)O (L(1) = N,N′-bis(3-methoxy-5-bromosalicylideneiminate) (2), {[Fe(qxcq)(CN)(3)][Mn(L(2))]}(2)·0.5H(2)O (L(2) = N,N′-ethylene-bis(3-ethoxysalicylideneiminate)) (3), [Fe(qxcq)(CN)(3)][Mn(L(3))] (L(3) = bis(acetylacetonato)ethylenediimine) (4), [Fe(qxcq)(CN)(3)][Mn(L(4))]·1.5MeOH·0.5CH(3)CN·0.25H(2)O (L(4) = N,N′-(1,1,2,2-tetramethylethylene)bis(salicylideneiminate)) (5), were prepared by assembling a new structurally characterized mer-tricyanoiron(III) molecular precursor (Ph(4)P)[Fe(qxcq)(CN)(3)]·0.5H(2)O (qxcq(−) = 8-(2-quinoxaline-2-carboxamido)quinoline anion) (1) and the corresponding manganese(III) Schiff base compound. Complexes 2and 3containa cyanide-bridged heterobimetallic dinuclear entity, which can be further dimerized by self-complementary H-bond interactions through the coordinated water molecule from one complex and the free O(4)unit from the adjacent complex. Complexes 4 and 5 area one-dimensional coordination polymer (CP) comprised of the repeated [Mn(Schiffbase)-Fe(qxcq)(CN)(3)] units. Complex 4 shows a linear-chain conformation with two trans-located cyano groups bridgingthe neighboring Mn units, while complex 5 is a zigzag-like 1D CP, where the two cyano groups in cis configurationfunction as bridges. In bothcomplexes 4 and 5, the inter-chain π–πstack interactions within the aromaticrings of cyanide precursor extend the 1D chain into the supermolecular 2D networks. The magnetic property has been experimentally studied and theoretically fitted over the four Fe(III)-Mn(III) complexes, revealing the antiferromagnetic interaction in complexes 2 and 4 and the unusual ferromagnetic coupling in complexes 3 and 5 between the Fe(III) ion and the Mn(III) ion bridged by the cyano group. Furthermore, the different magnetic coupling nature has been analyzed on the basis of the magneto-structure correlation of the mer-tricyanometallate-based Fe(III)-Mn(III) magnetic system.