Synthesis of Monomeric and Dimeric Copper(II) Carboxylates Bearing Polymerizable Groups and Their Performance in the Copolymerization with MMA

Abstract

The formation and characterization of the two binuclear copper(II) carboxylates Cu2(L)4·2CH3OH (1) and Cu(L)2·H2O·2pyridine (2) (L: methacrylate) are described which contain polymerizable groups. The dimeric Cu2(L)4·2CH3OH was prepared through reaction of methacrylic acid (LH) with basic copper carbonate in methanol solution. When 1 was dissolved in acetone and pyridine was added in excess to the solution, the binuclear complex turned into the mononuclear complex 2. 1 and 2 were characterized by UV−vis, IR, and elemental analysis, and the molecular structures were established by single-crystal X-ray diffraction studies. Both complexes were used in copolymerization with methyl methacrylate (MMA). Polymers containing the copper(II) carboxylates were prepared through radical copolymerization of 1 and 2 with MMA using azobis(isobutyronitrile) (AIBN) and benzoyl peroxide (BPO) as initiator. The obtained hybrid polymers were analyzed applying FT-IR, TGA, and size exclusion chromatography. All methods revealed an incorporation of both comonomers in the polymer backbone. Differences in the polymerization kinetics of the compounds can be explained by interactions of the primary initiating radicals with the copper complexes.

Cu(II) 4-phenoxybenzoate dimers and monomer coordinated by pyridines: Synthesis and crystal structures

“…In the other three paddle wheel dimers (2 The carboxylate plane is twisted respect to the plane containing the two O atoms the copper and the oxygen of the water molecule as usually found in similar structures [20,21,42,[46][47][48] (Fig. 5).…”

Reactivity of homoleptic and heteroleptic core paddle wheel Cu(II) compounds

“…Several parameters are established to distinguish between them: the value which range from 1 (D3h) to 0 (C4v) [30], the Lapical-M-Lbasal angle (102° for C4v) or the dihedral angles between the apical faces (53.1° for D3h, 75.7° for C4v) and the apical-basal faces (101.5° for D3h, 119.8° for C4v) [31]. All these compounds clearly exhibit a C4v geometry, taking into account these three factors: All the Cu-O and Cu-N distances for the three compounds are in the same order as described in the literature [17,[32][33][34][35][36] (Table 3). For 2, Cu(II) ion is 0.109 Å displaced out of the basal plane towards the axial site while in 3 and 4a, Cu(II) ion is displaced 0.029 Å and 0.062 Å, respectively.…”

“…Furthermore, the addition of the acetyl group in 4a allows the formation of supplementary interactions: one aliphatic hydrogen of the acetyl group interacts with the oxygen atom of the dioxole ring propagating the 1D chain along the c axis and forming 2D layers along the bc plane. Interestingly, there are few structures with similar 1D chain with a double H-bond interaction belonging from water -carboxylate [17,[32][33][34][35][36], which distinguishes compound 4a from the rest is the presence of three methanol and one occluded water molecules. Its supramolecular 2D squaregrid extended structure (Fig.…”

Synthesis and Crystal Structure of a Copper(II) Benzoate Complex Bearing a Bis-2,2′-Tetrahydrofuryl Peroxide Moiety

“…S1). Since the difference Δν = ν asν sym < 200 cm −1 , compound 2 probably shows a bidentate syn-syn configuration in the RCOO − ligand [43,44]. Based on Raman spectroscopy, the vibration of the ν(O-O) bond can be assigned at 850 cm −1 (Fig.…”