One‐Dimensional Coordination Polymers of Mn^II, Cu^II, and Zn^II Supported by Carboxylate‐Appended (2‐Pyridyl)alkylamine Ligands – Structure and Magnetism

Abstract

Four new complexes [MnII(L1OO)(H2O)][ClO4]·2H2O (1), [ZnII(L1OO)][ClO4]·2H2O (2), [CuII(L3OO)][CF3SO3]·H2O (3), and [ZnII(L3OO)][ClO4] (4) (L1OO– = 3‐[(2‐(pyridine‐2‐yl)ethyl){2‐(pyridine‐2‐yl)methyl}amino]propionate; L3OO– = 3‐[(2‐(pyridine‐2‐yl)ethyl){(dimethylamino)ethyl}amino]propionate) have been synthesized and characterized by elemental analysis, IR, and UV/Vis spectroscopy. Structural analysis revealed that 1, 3, and 4 are one‐dimensional chain‐like coordination polymers. In 1 distorted octahedral MnN3O3 and in 3 square‐pyramidal CuN3O2 coordination is satisfied by three nitrogen atoms and an appended carboxylate oxygen atom of the ligand, and an oxygen atom belonging to the carboxylate group of an adjacent molecule. In 4 trigonal bipyramidal ZnN3O2 coordination environment is provided by two nitrogen atoms and an appended carboxylate oxygen atom of the ligand in the equatorial plane, and the two axial positions are satisfied by a tertiary amine nitrogen and an oxygen atom belonging to the carboxylate group of an adjacent molecule. In 1 the MnII center is coordinated by an additional water molecule. In these complexes each monomeric unit is sequentially connected by syn‐anti carboxylate bridges. Temperature‐dependent magnetic susceptibilities for 1 and 3 are measured, revealing antiferromagnetic interactions through syn‐anti carboxylate bridges between the MII centers. Analysis of the crystal packing diagram reveals that in 1 extensive π–π stacking involving alternate pyridine rings of adjacent 1D chain exists, which eventually lead to the formation of a 2D network structure. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Two unique antiferromagnetic 3D frameworks with unusual CuII4 cluster and alternate CuII4 + CuII1 structural motif tuned by aromatic polycarboxylate coligand

“…Because the bonds angle of Cu-O-Cu is close to 90 (94.44 and 92.56 for Cu1-O7-Cu2 and Cu1-O3-Cu2, respectively), the superexchange pathways by double m 3 -OH and m 2 -h 2 :h 0 -COO À bridges transfer weak ferromagnetic coupling, which is overcompensated by the strong antiferromagnetic coupling mediating by the syn,syn-m 2 -h 1 :h 1 -COO À bridge and contributes essentially to a negative coupling constant. [39][40][41][42] For 2, the 1D covalent chain constructed from the alternate Cu II 4 clusters and the square-planar Cu II 1 cores becomes the magnetically active substructure of 2 (Fig. 2b).…”

First 3D heterotrimetallic Mn(II)–Cu(II)–K(I) polymer and three 3D Cu(II)/Mn(II) open network based on pyridine-2,3,5,6-tetracarboxylic acid

“…respectively. For complex 1, upon cooling, the μ eff value almost kept unchanged in the temperature of 30-300 K. The magnetic behavior follows the Curie-Weiss law with a Weiss constant of θ = − 3.33 K. The magnetic data of 1 have been analyzed using the following relation, χ M = (Ng 2 β 2 /kT) / (0.25 + 0.074975x + 0.075235x 2 ) / (1 + 0.9931x + 0.172135x 2 + 0.757825x 3 ) with x = |J|/kT [14]. The least-squares best-fit parameters for 1 are J = −5.622 cm −1 , g = 2.19.…”

Synthesis of Cu<SUP>II</SUP>-Nanocrystal Coordination Polymer by Microemulsion Method. Straightforward Experiment of Nanomaterial Synthesis for Science High School Students

“…Di(2-pyridylmethyl)alkylamine-appended carboxylate ligands (CnCOOH, n = number of methylene group in the alkyl chain) is an appropriate ligand to react with metal ion to achieve coordination polymers (CPs) [7]. To date, the majority of CPs utilizing CnCOOH have been reported to form one-dimensional (1D) structures [8].…”