Influence of the Metal Ion on the Topology and Interpenetration of Pyridylvinyl(benzoate) Based Metal–Organic Frameworks

Abstract

A family of four M­(II)-metal–organic frameworks of general formula {[M x (pvb)2x ]­·y(dmf)} n (M = Cu, 1; M = Co, 2; M = Ni, 3; M = Mn, 4), based on the bis­{4-[2-(4-pyridyl)­ethenyl]} benzoic acid (Hpvb) ligand, were obtained. 1 exhibits a 5-fold interpenetrated lvt framework, 2 and 3 a 7-fold interpenetrating dia framework, and 4 a 2-fold interpenetrated dmc framework. Magnetic properties of 1–4 have been investigated. 1 was analyzed by a Curie–Weiss model, while 2 and 3 where analyzed by a zero-field splitting model due to the very long metal–metal distances, which results in very weak antiferromagnetic interactions. The coupling pathway in 4 was done by carboxylate bridges instead of the pvb pathway, affording a short metal–metal separation that was analyzed by a isotropic Heisenberg spin Hamiltonian for a linear trinuclear Mn­(II) cluster. The different metal coordination modes and geometries, along with template effects induced by the solvent, play an important role in the formation of distinctive structural topologies.

Ortho Effects of Tricarboxylate Linkers in Regulating Topologies of Rare-Earth Metal–Organic Frameworks

“…1 H NMR spectrum indicates that dimethylamine cations serve as the counter cations to balance the negative charge of integral framework (Figure S46). Trinuclear clusters are common for d-block metal-based MOFs. − However, only a limited number of RE 3 clusters have been reported, most of which feature linear or bent geometries. − To our knowledge, one rare example of trigonal prismatic RE 3 clusters was observed in a MOF named JXNU-3 composed of 15-c nonanuclear and 9-c trinuclear clusters . Han, Gu, and co-workers reported several robust RE MOFs bearing 6-c trinuclear clusters in 2017 .…”

Structural and Magnetic Properties of a Pyridyl(vinyl)benzoate-Based Metal–Organic Framework with Iron(II) as Spin Carrier

“…Considering the structures deposited in the CCDC database, a survey of 41 structures with this ligand shows an average angle of 17.7°, ranging from a maximum of 53.3° to a minimum of 0°. In contrast with the roughly planar structure of the pvb – ligand (or its derivative, disregarding the carboxylate group in both cases), in other coordination compounds, − ,, the pvb – structure in 1 is highly distorted, as noted by the presence of a twist angle between the pyridyl ring and the aromatic ring of the benzoic moiety of 37.85° and 67.61° for each pvb – anion in the asymmetric unit, respectively (Figure S5).…”

Design and Self-Assembly of Ferrocene-Functional Heterometal–Oxo Clusters with the M(III)4O4 Cubane Core

“…Compared with compound 2, the dimerization behavior of compound 4 actually caused the Cu•••Cu distance to be extended from 5.048 to 11.146 Å, which may weaken the interaction between Cu ions and lead to changes in magnetic interactions at low temperatures. 45 In 1977, Toulouse and Villain proposed the concept of frustration, and the competitive magnetic system used in magnetic coupling is called the spin frustration system. 46 Tetrahedral magnetic interaction model is formed in the clusters of the M 4 O 4 cubane cluster core, and these tetrahedral clusters are almost isolated from each other.…”

“…These close distances result in coupling between the Cu 2+ ions. Compared with compound 2 , the dimerization behavior of compound 4 actually caused the Cu···Cu distance to be extended from 5.048 to 11.146 Å, which may weaken the interaction between Cu ions and lead to changes in magnetic interactions at low temperatures …”