Cyanide‐Bridged Complexes of Transition Metals: A Molecular Magnetism Perspective

[MnIII(salen)]6[FeIII(bpmb)(CN)2]6⋅7 H2O: A Cyanide‐Bridged Nanosized Molecular Wheel

Dicyanometalate chemistry: A type of versatile building block for the construction of cyanide-bridged molecular architectures

The azido-bridged manganese complex of formula [Mn(tptz)(mu(1,1)-N3)2]n [1; tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine] has been synthesized and characterized by single-crystal X-ray diffraction analysis and a low-temperature magnetic study. The complex 1 crystallizes in the orthorhombic space group Pbcn, with a = 17.911(5) A, b = 15.804(5) A, c = 6.6538(18) A, and Z = 4. The Mn atoms are coordinated by three N atoms of the tptz ligands and connected to each other by double end-on (EO) azide ligands, forming a neutral 1D chain. The adjacent 1D chains are connected by face-to-face pi-pi-stacking interactions and C-H...pi interactions of pyridine rings of the tptz ligands, which leads to the formation of a supramolecular 2D sheet structure. Temperature- and field-dependent magnetic analyses reveal dominant intrachain ferromagnetic interactions with EO azide-bridge and weak interchain antiferromagnetic interactions with overall metamagnetic behavior having 3D magnetic ordering at 2.7 K. The critical field is approximately 80 G, at which the interlayer antiferromagnetic ground-state switches to a ferromagnetic state.

Weak metamagnetic-like 1D manganese(II) complex with a double mu(1,1)-azido bridge: a structure and magnetic study.

Two new cyano-bridged heterobinuclear complexes, [MnII(phen)2Cl][FeIII(bpb)(CN)2]·0.5CH3CH2OH·1.5H2O (1) and [MnII(phen)2Cl][CrIII(bpb)(CN)2]·2H2O (2) [phen = 1,10-phenanthroline; bpb2- = 1,2-bis(pyridine-2-carboxamido)benzenate], and four novel azido-bridged Mn(II) dimeric complexes, [Mn2(phen)4(μ1,1-N3)2][MIII(bpb)(CN)2]2·H2O [M = Fe (3), Cr (4), Co (5)] and [Mn2(phen)4(μ1,3-N3)(N3)2]BPh4·0.5H2O (6), have been synthesized and characterized by single-crystal X-ray diffraction analysis and magnetic studies. Complexes 1 and 2 comprise [Mn(phen)2Cl]+ and [M(bpb)(CN)2]- units connected by one cyano ligand of [M(bpb)(CN)2]-. Complexes 3−5 are doubly end-on (EO) azido-bridged Mn(II) binuclear complexes with two [M(bpb)(CN)2]- molecules acting as charge-compensating anions. However, the Mn(II) ions in complex 6 are linked by a single end-to-end (EE) azido bridging ligand with one large free BPh4- group as the charge-balancing anion. The magnetic coupling between Mn(II) and Fe(III) or Cr(III) in complexes 1 and ...

Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)2]2+ building block: syntheses, crystal structures, and magnetic properties.

A dicyano-containing [Fe(bpb)(CN)2]- building block has been employed for the synthesis of cyano-bridged heterometallic NiII−FeIII complexes. The presence of steric bpb2- ligand around the iron ion results in the formation of low-dimensional species:  five are neutral NiFe2 trimers and three are one-dimensional (1D). The structure of the 1D complexes consists of alternating [NiL]2+ and [Fe(bpb)(CN)2]- generating a cyano-bridged cationic polymeric chain and the perchlorate as the counteranion. In all complexes, the coordination geometry of the nickel ions is approximately octahedral with the cyano nitrogen atoms at the trans positions. Magnetic studies of seven complexes show the presence of ferromagnetic interaction between the metal ions through the cyano bridges. Variable temperature magnetic susceptibility investigations of the trimeric complexes yield the following JNiFe values (based on the spin exchange Hamiltonian H = −2JNiFeSNi(SFe(1) + SFe(2)):  JNiFe = 6.40(5), 7.8(1), 8.9(2), and 6.03(4) cm-1, ...

[Fe(bpb)(CN)2]- as a Versatile Building Block for the Design of Novel Low-Dimensional Heterobimetallic Systems: Synthesis, Crystal Structures, and Magnetic Properties of Cyano-Bridged FeIII−NiII Complexes [(bpb)2- = 1,2-Bis(pyridine-2-carboxamido)benzenate]

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[Fe(bpb)(CN)2]- as a Versatile Building Block for the Design of Novel Low-Dimensional Heterobimetallic Systems: Synthesis, Crystal Structures, and Magnetic Properties of Cyano-Bridged FeIII−NiII Complexes [(bpb)2- = 1,2-Bis(pyridine-2-carboxamido)benzenate]

Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)2]2+ building block: syntheses, crystal structures, and magnetic properties.