Dataset Information

Synthesis, Structures, and Magnetism of Four One-Dimensional Complexes Using [Ni(CN)₄]^2- and Macrocyclic Metal Complexes.

ABSTRACT: Four one-dimensional complexes, denoted as [NiL₁][Ni(CN)₄] (1), [CuL₁][Ni(CN)₄] (2), [NiL₂][Ni(CN)₄]·2H₂O (3), and [CuL₂][Ni(CN)₄]·2H₂O (4) (L₁ = 1,8-dimethyl-1,3,6,8,10,13-hexaaza-cyclotetradecane; L₂ = 1,8-dipropyl-1,3,6,8,10,13-hexaazacyclotetradecane) were synthesized by reacting nickel/copper macrocyclic complexes with K₂[Ni(CN)₄]. Subsequently, the synthesized complexes were characterized using elemental analysis, infrared spectroscopy analysis, thermogravimetric analysis, and X-ray powder diffraction. Single-crystal structure analysis revealed that the Ni(II)/Cu(II) atoms were coordinated by two nitrogen atoms from [Ni(CN)₄]^2- with four nitrogen atoms from a macrocyclic ligand, forming a six-coordinated octahedral coordination geometry. Nickel/copper macrocyclic complexes were bridged by [Ni(CN)₄]^2- to construct one-dimensional chain structures in 1-4. The characterization results showed that the four complexes obeyed the Curie-Weiss law with a weak antiferromagnetic exchange coupling.

SUBMITTER: Ou G

PROVIDER: S-EPMC10254484 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature

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Synthesis, Structures, and Magnetism of Four One-Dimensional Complexes Using [Ni(CN)4]2- and Macrocyclic Metal Complexes.

Ou Guangchuan G Wang Qiong Q Tan Yingzhi Y Zhou Qiang Q

Molecules (Basel, Switzerland) 20230602 11

Four one-dimensional complexes, denoted as [NiL1][Ni(CN)4] (1), [CuL1][Ni(CN)4] (2), [NiL2][Ni(CN)4]·2H2O (3), and [CuL2][Ni(CN)4]·2H2O (4) (L1 = 1,8-dimethyl-1,3,6,8,10,13-hexaaza-cyclotetradecane; L2 = 1,8-dipropyl-1,3,6,8,10,13-hexaazacyclotetradecane) were synthesized by reacting nickel/copper macrocyclic complexes with K2[ ...[more]

PMID: 37299003

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Project description:The new heterometallic compounds, [{Cu(pn)2}2Ni(NCS)6]n·2nH2O (1), [{CuII(trien)}2Ni(NCS)6CuI(NCS)]n (2) and [Cu(tren)(NCS)]4[Ni(NCS)6] (3) (pn = 1,2-diaminopropane, trien = triethylenetetramine and tren = tris(2-aminoethylo)amine), were obtained and characterized by X-ray analysis, IR spectra, XAS and magnetic measurements. Compounds 1, 2 and 3 show the structural diversity of 2D, 1D and 0D compounds, respectively. Depending on the polyamine used, different coordination polyhedron for Cu(II) was found, i.e., distorted octahedral (1), square pyramidal (2) and trigonal bipyramidal (3), whereas coordination polyhedron for nickel(II) was always octahedral. It provides an approach for tailoring magnetic properties by proper selection of auxiliary ligands determining the topology. In 1, thiocyanate ligands form bridges between the copper and nickel ions, creating 2D layers of sql topology with weak ferromagnetic interactions. Compound 2 is a mixed-valence copper coordination polymer and shows the rare ladder topology of 1D chains decorated with [CuII(tren)]2+ antennas as the side chains attached to nickel(II). The ladder rails are formed by alternately arranged Ni(II) and Cu(I) ions connected by N2 thiocyanate anions and rungs made by N3 thiocyanate. For the Cu(I) ions, the tetrahedral thiocyanate environment mixed N/S donor atoms was found, confirming significant coordination spheres rearrangement occurring at the copper precursor together with the reduction in some Cu(II) to Cu(I). Such topology enables significant simplification of the magnetic properties modeling by assuming magnetic coupling inside {NiIICuII2} trinuclear units separated by diamagnetic [Cu(NCS)(SCN)3]3- linkers. Compound 3 shows three discrete mononuclear units connected by N-H…N and N-H…S hydrogen bonds. Analysis of XAS proves that the average ligand character and the covalency of the unoccupied metal d-based orbitals for copper(II) and nickel(II) increase in the following order: 1 → 2 → 3. In 1 and 2, a weak ferromagnetic coupling between copper(II) and nickel(II) was found, but in 2, additional and stronger antiferromagnetic interaction between copper(II) ions prevailed. Compound 3, as an ionic pair, shows, as expected, a spin-only magnetic moment.

Dataset Information

Synthesis, Structures, and Magnetism of Four One-Dimensional Complexes Using [Ni(CN)₄]^2- and Macrocyclic Metal Complexes.

Publications

Synthesis, Structures, and Magnetism of Four One-Dimensional Complexes Using [Ni(CN)<sub>4</sub>]<sup>2-</sup> and Macrocyclic Metal Complexes.

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