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

1
College of Chemical and Chemical Engineering, Shandong University of Technology, Zibo 255049, China
2
College of Chemical and Chemical Engineering, Liaocheng University, Liaocheng 252059, China
3
Dongchang College of Liaocheng University, Liaocheng 252059, China
*
Author to whom correspondence should be addressed.
Polymers 2019, 11(10), 1585; https://doi.org/10.3390/polym11101585
Received: 17 August 2019 / Revised: 22 September 2019 / Accepted: 22 September 2019 / Published: 27 September 2019
Four cyanide-bridged FeIII–MnIII complexes {[Fe(qxcq)(CN)3][Mn(L1)(H2O)]}[Mn(L1)(H2O)(CH3OH)](ClO4)·1.5MeOH·0.5H2O (L1 = N,N′-bis(3-methoxy-5-bromosalicylideneiminate) (2), {[Fe(qxcq)(CN)3][Mn(L2)]}2·0.5H2O (L2 = N,N′-ethylene-bis(3-ethoxysalicylideneiminate)) (3), [Fe(qxcq)(CN)3][Mn(L3)] (L3 = bis(acetylacetonato)ethylenediimine) (4), [Fe(qxcq)(CN)3][Mn(L4)]·1.5MeOH·0.5CH3CN·0.25H2O (L4 = N,N′-(1,1,2,2-tetramethylethylene)bis(salicylideneiminate)) (5), were prepared by assembling a new structurally characterized mer-tricyanoiron(III) molecular precursor (Ph4P)[Fe(qxcq)(CN)3]·0.5H2O (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 O4unit 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. View Full-Text
Keywords: coordination polymer; cyanide-bridged; new building block; single crystal structure; magnetism coordination polymer; cyanide-bridged; new building block; single crystal structure; magnetism
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Lan, W.; Hao, X.; Dou, Y.; Zhou, Z.; Yang, L.; Liu, H.; Li, D.; Dong, Y.; Kong, L.; Zhang, D. Various Structural Types of Cyanide-Bridged FeIII–MnIII Bimetallic Coordination Polymers (CPs) and Polynuclear Clusters Based-on A New mer-Tricyanoiron(III)Building Block: Synthesis, Crystal Structures, and Magnetic Properties. Polymers 2019, 11, 1585.

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