Ni^II, Mn^II, and Co^II Coordination Polymers with 1,4-Naphthalenedicarboxylic Acid Exhibiting Metamagnetic and Antiferromagnetic Behaviors

Abstract

Three novel compounds, [Ni4(1,4-ndc)3­(OH)2(H2O)2­·2.5H2O] n (1), {[Mn2(1,4-ndc)2­(OAc)]­(C5MIm)­·0.5H2O} n (2), and {[Co3(1,4-ndc)4­(H2O)4]­(C5MIm)2­·2H2O} n (3), were hydro-/solvothermally prepared with the corresponding acetate, 1,4-H2ndc (1,4-H2ndc = 1,4-naphthalenedicarboxylic acid) and different auxiliaries such as C5MImBr (C5MImBr = 1-pentyl-3-methylimidazolium bromide) or 2,4-diamino-6-methyl-1,3,5-triazine. Compound 1 composes of one three-dimensional (3D) network, where one rare nickel chain is constructed through NiII ions bridged by μ3-OH– groups, μ3-η2:η1 and μ2-η1:η1 carboxyl groups from 1,4-ndc2– groups as well as coordination water molecules. In compound 2, MnII ions are connected by μ4-η1:η1:η1:η1 1,4-ndc2– groups and μ2-η1:η1 acetate radicals, forming a 3D framework. For compound 3, a [Co3(CO2)4­(H2O)4] unit is observed, which is further bridged by μ2-η1:η0:η1:η0 and μ4-η1:η1:η1:η1 1,4-ndc2– groups and ultimately results in forming a 3D structure. It demonstrates compounds 1–3 can be noted as pcu, lon, and the highly connected bcu topologies by topology analysis, respectively. A thorough magnetic study of 1 reveals the metamagnetic behavior, mainly resulting from the unique one-dimensional NiII chain. Comparatively, magnetic analyses of 2 and 3 suggest the presence of the antiferromagnetic interactions with the best fitting magnetic susceptibility data for 2 (J = −0.85 cm–1 and g = 2.1) at 10–300 K.

Construction of Four γ-Octamolybdate-Based Coordination Polymers Using Linear Nitrogen Heterocyclic Ligands for Proton Conduction

“…Nitrogen heterocyclic ligands have attracted many researchers′ attention because they not only possess definite active sites, rich coordination patterns, and strong coordination capabilities, but also make for the formation of hydrogen bonds and π···π stacking interactions. − Up to now, it has been discovered that imidazole, triazole, pyridine ligands, and their derivatives have been widely utilized in the synthesis of POM-based compounds, such as the linear and V-type ligands, among others. − Compared with V-type ligands, linear ligands exhibit more defined coordination patterns, facilitating the intentional design and construction of desired compounds. Our group has conducted several studies using linear nitrogen heterocyclic ligands and synthesized some compounds, underscoring that linear organic ligands are an excellent choice. , …”

“…Our group has conducted several studies using linear nitrogen heterocyclic ligands and synthesized some compounds, underscoring that linear organic ligands are an excellent choice. 40,41 In this work, we utilized the linear organic ligand 1-(4H-1,2,4triazole-4-yl)-4-(imidazole-1-yl) benzene (tib), which simultaneously possesses imidazole and triazole rings at both ends of a benzene ring, and the existence of multiple coordination sites on this ligand is conducive to the formation of diverse coordination modes. Additionally, the uncoordinated nitrogen atoms are easily protonated and can form hydrogen bonds with water molecules or oxygen atoms in POMs, which is beneficial for proton conduction.…”

Newly designed Mn (III)–W(V) bimetallic assembly built by manganese (III) Schiff–base and octacyanotungstate(V) building blocks: Structural topologies, and magnetic features

“…In the past few decades, considerable efforts have been given to create new molecule–based magnets via a combination of dissimilar paramagnetic metal ions within the same molecular unit, as the magnetic interaction between these spin carriers can be easily controlled to obtain materials with desired properties. [ 1–13 ] A lot of large and ultra–large complexes with controlled nuclearity based on d – and f –metal centers have been synthesized as SMMs. One such example is a family of heterometallic architecture containing polycyanometallates of Mo(V), Nb(V), or W(V), [ 14 ] which have been employed to synthesize cyano–bridged magnetic complexes with fascinating magnetic properties, such as the T C 's magnets, [ 15–18 ] single–molecule magnets (SMMs), [ 19–25 ] and single chain magnets SCMs).…”

Toward a Rational Design of 3d-4f Heterometallic Coordination Polymers based on Mixed Valence Copper Centers

“…In recent years, coordination polymers (CPs) have been widely studied in materials science due to their excellent chemical and physical properties, such as porosity, chemical and thermal stability, and catalytic activity, making the rational design of new CPs a continuous challenge for researchers. − In this sense, the combination of two different metal cations in the same structure, such as first row transition (3d) and lanthanide (4f) cations, has been used as a strategy to obtain new CPs with novel structures and potential applications such as magnetic refrigeration, solid state luminescence, and catalysis. − Compared with the lanthanide series, first row transition metals have a richer chemistry as a consequence of the various oxidation states (from +1 to +7) and coordination geometries. Specifically, Cu I and Cu II cations can adopt a wide variety of coordination geometries (linear, trigonal, tetrahedral, trigonal bipyramid, square base pyramid, octahedral) as compared to other transition metal ions.…”