Cation Exchange in Layered Copper(II) Coordination Polymers

Abstract

The covalently linked anionic layers of a series of CuII 2,3‐pyridinecarboxylate anions containing organic cations are characterized. Depending on the cations, mononuclear, dinuclear or polynuclear complexes are formed. The complex with adeninium cations is mononuclear, whereas the complexes bearing cations of 4‐aminobenzylamine, 1,5‐diaminopentane, and 5‐aminoquinoline are dinuclear, and complexes bearing cations of isopropylamine, ethylenediamine, 1,8‐diaminooctane, N,N,N′,N′‐tetramethylethylenediamine, tris(2‐aminoethyl)amine, 1,4‐diazabicyclo[2.2.2]octane, imidazole, pyridine, 8‐hydroxyquinoline, and cytidine are coordination polymers. All of the complexes other than the one bearing tris(2‐aminoethyl)amine cations have lamellar structures. The polynuclear complex anion with tris(2‐aminoethyl)amine trications exhibits an unusual –3 charge for the polynuclear anionic nodes. The 1H,9H‐adeninium cationic dimers are stabilized in the interstices of mononuclear CuII quinolinate complex anions. The interlayer separations in the layered polymers varied from 8.5 to 15.9 Å and are guided by the cations. Biologically relevant cytidinium cations are trapped in the layers of polymeric anions. The complexes bearing organocations undergo exchange of the organic cations with alkali, alkaline earth, or transition metal ions or with smaller cations without disturbance of the polymeric inorganic layer. The exchange of the cytidinium cations by metal ions resulted in polymeric complexes in which the cationic organic layer is replaced by a layer of aquated metal cations. The thermochemical properties, electron paramagnetic resonance (EPR) spectroscopy, and solid‐state conductance of the complexes are described.

Structure of a dinuclear cadmium complex with 2,2′-bipyridine, monodentate nitrate and 3-carboxy-6-methylpyridine-2-carboxylate ligands: intramolecular carbonyl(lone pair)...π(ring) and nitrate(π)...π(ring) interactions

“…A search in the CSD (Version 5.3; Groom & Allen, 2014) disclosed ca 200 complexes displaying diverse topologies, viz. monomers (Gao et al, 2010;Drew et al, 1971), dimers (Shankar et al, 2013), oligomers (Yu et al, 2003) as well as one-dimensional (Semerci et al, 2014), two-dimensional (Ç olak et al, 2011) and three-dimensional (Kanoo et al, 2012) polymers. In the vast majority of cases the ligand adopts an N,O-chelating mode, although there are a few exceptions to this where the binding sites attach to different metal atoms (e.g.…”

Synthesis, structure and characterization of a layered coordination polymer based on Zn(ii) and 6-(methylmercapto)purine

“…As nucleobases contain multiple donor sites, they can act as ligands in coordination networks useful in medicine, industry, agriculture and coordination chemistry. 26 There are several examples of LCPs based on Zn [27][28][29][30][31][32][33][34][35][36][37] or nucleobases, [38][39][40][41][42][43][44] but just a few based on the Zn and nucleobase combination. 45,46 Here, we report the synthesis and characterization of a new LCP named UZAR-S12 (henceforth referred to as 1).…”

Synthesis, structures, thermal and magnetic properties of two bis(oxalato)cuprate(II) hybrid salts containing pyridinium derivative cations

“…Moreover, these materials may be used as model compounds for ferroelectric and ferroelastic applications [11,12]. In such salts, self-assembly processes are governed not only by intrinsic features of each ionic component, but also by non-covalent interactions including hydrogen bonds, ionic interactions, π-π and/or van der Waals interactions [13,14].…”