Discrete Complexes and One-Dimensional Coordination Polymers with [Cu(II)(2,2′-bpy)]²⁺ and [Cu(II)(phen)]²⁺ Corner Fragments: Insight into Supramolecular Structure and Optical Properties

Abstract

The combination of [Cu­(II)­(2,2′-bpy)]2+ and [Cu­(II)­(phen)]2+ (2,2′-bpy = 2,2′-bipyridine; phen = 1,10-phenanthroline) corner fragments predisposed to π–π stacking interactions with bridging ligands 4,4′-bipyridine (4,4′-bpy), 4,4′-bipyridinethane (bpe), and 4,4′-bipyridinepropane (bpp) in the presence of linear SCN–, or tetrahedral ClO4 – or BF4 – inorganic anions and/or organic acetate anion provides access to a series of new metal–organic materials including non-centrosymmetric polymeric chains, whose architectures were confirmed through single crystal X-ray crystallographic analysis. The nine reported compounds comprise one mononuclear complex, [Cu­(2,2′-bpy)2­(CH3COO)]­(SCN)­(H2O) (1), three binuclear complexes, [Cu2(2,2′-bpy)2­(CH3COO)2­(SCN)2(4,4′-bpy)]­0.5dmf (2), [Cu2(phen)2­(CH3COO)2­(SCN)2­(bpe)] (3), [Cu2(phen)2­(SCN)4­(bpe)] (4), and five one-dimensional coordination polymers, {[Cu­(2,2′-bpy)­(4,4′-bpy)­(ClO4)2]­(H2O)} n (5), {[Cu­(phen)­(4,4′-bpy)­(BF4)2]­(H2O)} n (6), {[Cu­(2,2′-bpy)­(ClO4)­(H2O)­(bpp)]­(ClO4)} n (7), {[Cu­(phen)­(ClO4)­(dmf)­(bpp)]­(ClO4)} n (8), and {[Cu­(phen)­(bpp)­(BF4)2]­[Cu­(phen)­(bpp)2­(BF4)]­(BF4)} n (9). Coordination polymers represent the neutral (5, 6), cationic (7, 8), or a blend of neutral and cationic chains (9), and differ by the Cu­(II) coordination cores, conformations of the bridging ligands, and functions of the anions. All compounds except 7 reveal cooperative π–π stacking interactions of corner fragments. As expected for the paramagnetic d9 Cu­(II) complexes, the polymeric solids show the luminescence quenching. The second order nonlinear optical properties of powders of the non-centrosymmetric compounds 8 and 9 were also tested.

One-dimensional copper(II) coordination polymers based on 1,3-bis(pyridin-4-yl)propane and diimine ligands

“…neighbouring Cu II cations connected by the dpp spacer in the two chains are 13.6162 (13) and 13.7434 (13) Å . The shape of the chain is essentially similar to that of the analogue {[Cu(ClO 4 )(bpy)(H 2 O)(dpp)]ClO 4 } n (Melnic et al, 2016), with water and ClO 4 À anions at axial positions. The [Cu(NO 3 )(bpy)(dpp)(H 2 O)]NO 3 building block of CP 1 contains two hydrogen-bond donors and five hydrogen-bond acceptors.…”

Transformations of Polymers of 4,4'-Dipyridyl and Cobalt(II) and Manganese(II) Cymantrenates in the Presence of N-Donors of Different Denticity

“…[28]; M = Cu: Q = bpy, An = η-OClO 3 ; Q = Phen, An = η-OClO 3 , ClO 4 [29]; Q = Phen, An = η-OSO 2 CF 3 [30]; Q = bpy, An = η-ONO 2 [31]; Q = bpy, L = 2H 2 O, An = NO 3 [32]; Q = bpy, An = η-OClO 3 , H 2 O(solv. ); Q = bpy, An = η-FBF 3 , H 2 O(solv) [33]; M = Co: Q = Phen, An = η-PhPO 3 [32]) were isolated. Note that in all the above examples, the complexes were synthesized as a result of the reactions of Phen/bpyMAn 2 with dipy, in contrast to the preparation of 1-3, when the starting compounds were polymers.…”

Tunable Supramolecular Nanoarchitectures Constructed by the Complexation of Diphenanthro‐24‐Crown‐8/Cesium(I) with Nickel(II) and Silver(I) Ions

“…As π-stacking of phenanthroline derivatives and the binding character of 24-crown-8 for Cs + had been well established, [6] it was possible for DPC to form nanostructures by self-assembly and change its morphology by complexation with Cs + . As anticipated, self-assembly DPC did yield fiber-like structures after the evaporation of solvent (Scheme 1, Figure 1a,b).…”