Pillaring Role of 4,4 '-Azobis(pyridine) in Substituted Malonate-Containing Manganese(II) Complexes: Syntheses, Crystal Structures, and Magnetic Properties
Deniz, M; Hernandez-Rodriguez, I; Pasan, J; Fabelo, O; Canadillas-Delgado, L; Yuste, C; Julve, M; Lloret, F; Ruiz-Perez, C
| HERO ID | 3705115 |
|---|---|
| In Press | No |
| Year | 2012 |
| Title | Pillaring Role of 4,4 '-Azobis(pyridine) in Substituted Malonate-Containing Manganese(II) Complexes: Syntheses, Crystal Structures, and Magnetic Properties |
| Authors | Deniz, M; Hernandez-Rodriguez, I; Pasan, J; Fabelo, O; Canadillas-Delgado, L; Yuste, C; Julve, M; Lloret, F; Ruiz-Perez, C |
| Journal | Crystal Growth & Design |
| Volume | 12 |
| Issue | 9 |
| Page Numbers | 4505-4518 |
| Abstract | Six new manganese(II) complexes of formulas [Mn-2(Rmal)(2)(H2O)(2)(azpy)](n) (1-3), [Mn(Phmal)(H2O)-(azpy)](n) (4), [Mn-2(Et(2)mal)(2)(H2O)(4)(azpy)(2)](n) (5), and [Mn(Bzmal)(H2O)(3)(azpy)] (6) [azpy = 4,4'-azobispyridine (1-6), Rmal = methylmalonate (Memal) (1), dimethylmalonate (Me(2)mal) (2), and butylmalonate (Butmal) (3), Phmal = phenylmalonate (4), Et(2)mal = diethylmalonate (5), and Bzmal = benzylmalonate (6)] were synthesized and structurally characterized by single-crystal X-ray diffraction. Complexes 1-3 are three-dimensional compounds whose structure consists of corrugated layers of manganese(II) linked through syn-anti carboxylate (Rmal) bridges, which are pillared through the bis-monodentate azpy molecule. Complex 4 has a layered structure of manganese(II) ions connected by carboxylate (Phmal) bridges in the syn-anti coordination mode as in 1-3, the azpy group acting here as a terminally bound monodentate ligand. The structure of 5 consists of Et(2)mal-Mn(II) neutral chains linked through the azpy ligand, giving rise to a complex three-dimensional network. Complex 6 is constituted by neutral [Mn(Bzmal)(H2O)(3)(azpy)] mononuclear units, which are interlinked through O-H center dot center dot center dot O, O-H center dot center dot center dot N, and pi-pi type intermolecular interactions to afford a three-dimensional supramolecular structure. The topological analysis of these crystallographic structures shows the occurrence of four different nets: a (3,4)-connected InS-type (1-3), a binodal layered hcb (4), a uninodal CdS-type (5), and a (4,5)-connected tcs topology (6). The magnetic properties of 1-5 were investigated in the 2.0-300 K temperature range. Overall antiferromagnetic behavior occurs in 1-4 with susceptibility maxima in the range 2.8-5.5 K, the exchange pathway being provided by the syn-anti carboxylate (substituted malonate) bridge [manganese-manganese separation in the range 5.4365(3)-5.5274(1) angstrom]. Very weak antiferromagnetic interactions are observed in 5 through the trans-bis-monodentate Et(2)mal ligand, the intrachain manganese-manganese separation being 7.328(3) angstrom. The much larger manganese-manganese separation through the bis-monodentate azpy ligand in 1-5 (values greater than 13.5 angstrom) accounts for the lack of any significant magnetic interaction though this extended bridge. |
| Doi | 10.1021/cg300670a |
| Wosid | WOS:000308279900029 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |