Abstract
Three metal–organic complexes with two anthracene-based bulky backbone ligands 9,10-dioxo-9,10-dihydroanthracene-1,5-dicarboxylic acid (H2 L 1) and 2-phenylquinoline-4-carboxylic acid (HL 2), namely {[Mn(L 1)0.5(L 1)0.5(phen)(H2O)2](H2O)1.5}∞ (1), [Mn2(L 2)4(phen)2(H2O)2](H2O)2 (2) and [Cd3(L 2)2(pp)2Cl4]∞ (3) (phen = 1,10-phenanthroline, pp = 3-(2-pyridyl)pyrazole), have been synthesized and characterized. X-ray single-crystal diffraction indicates that H2 L 1 adopts a bis-monodentate bridging mode in complex 1, whereas HL 2 adopts monodentate and bidentate bridging modes in 2 and a tridentate bridging mode in 3. The chelating ligands phen and pp give rise to a 1D zigzag chain in complexes 1 and 3, and a binuclear structure in 2, by preventing the formation of higher-dimensional structures. Notably, the anions play an important role in the structure of complex 3. In addition, the magnetic and luminescent properties of these complexes were investigated. Three metal–organic compounds, showing a 1D zigzag chain, a binuclear structure and a 1D zigzag chain, have been successfully constructed by using 9,10-dioxo-9,10-dihydroanthracene-1,5-dicarboxylic acid and 2-phenylquinoline-4-carboxylic acid, together with incorporating auxiliary bridging ligands 1,10-phenanthroline or 3-(2-pyridyl)pyrazole. The present results reveal that chelated ligands phen and pp play an important role in the formation of frameworks of 1–3, which prevent the formation of higher-dimensional structures. Moreover, intense luminescent emissions of 1–3 were attributed to the LLCT of corresponding ligand. And antiferromagnetic coupling interaction exists between the binuclear MnII ions in 2.
Highlights
The design of metal–organic crystalline materials has attracted considerable attention due to their interesting architectures and applications in optics, magnetism, gas storage, ion exchange and catalysis [1, 2]
X-ray singlecrystal diffraction indicates that H2L1 adopts a bis-monodentate bridging mode in complex 1, whereas HL2 adopts monodentate and bidentate bridging modes in 2 and a tridentate bridging mode in 3
The anions play an important role in the structure of complex 3
Summary
The design of metal–organic crystalline materials has attracted considerable attention due to their interesting architectures and applications in optics, magnetism, gas storage, ion exchange and catalysis [1, 2]. Several anthracene-based bulky backbone ligands, namely acridine-9-carboxylic acid [14], anthracene-9-carboxylic acid [15], anthracene-9,10-dicarboxylic acid [15, 16] and anthracene-1,5-dicarboxylic acid [16], were used to construct a range of metal coordination compounds, showing interesting luminescent, magnetic and gas adsorption properties. By contrast, anthracenebased bulky backbone ligands, such as phenylquinoline[17, 18] and anthraquinone-based carboxylic acids [19, 20], have not yet been widely studied. We have selected two anthracene-based bulky backbone ligands, 9,10-dioxo-9,10-dihydroanthracene-1,5-dicarboxylic acid (H2L1) and 2-phenylquinoline-4-carboxylic acid (HL2) (Fig. 1), together with 1,10-phenanthroline (phen) or 3-(2-. Pyridyl)pyrazole (pp) as auxiliary ligands, to construct three MnII and CdII coordination compounds, namely {[Mn(L1)0.5(L1)0.5(phen)(H2O)2](H2O)1.5}? IR (KBr pellet, cm-1): 3,374 s(br), 3,075 w, 1,689 s, 1,567 s, 1,517 s, 1,466 m, 1,438 w, 1,407 s, 1,326 s, 1,275 s, 1,232 w, 1,167 w, 1,137 w, 1,094 w, 1,008 w, 865 w, 844 w, 827 m, 807 w, 783 w, 770 m, 727 m, 711 s, 686 m, 614 w, 421 w
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