Abstract
A series of lanthanide sulfates coordination complexes, Ln2(SO4)3(H2O)8 (Ln = Pr (1), Nd (2), Tb (3), Sm (4), Dy (5), Gd (7), Ho (8)), and EuK(SO4)2 (6), were constructed by the reaction in situ of lanthanide ions (Ln3+) with flexible dodecanedioic acid and rigid aromatic 5-sulfosalicylic acid under hydrothermal conditions. All of them were characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. The crystal structures and coordination modes of metal centers and sulfate ions, as well as the novel reaction mechanism and different conditions of lanthanide ions and 5-sulfosalicylic acid to form the series of lanthanide sulfate complexes, were discussed in detail. Solid-state properties for these crystalline materials, such as thermal stability and powder X-ray diffraction have been investigated. Additionally, the photoluminescent characterizations of the complexes 3, 4, 5 and 6, and the catalytic properties of all the complexes about cyclohexane being oxidized into cyclohexanone/cyclohexanol were investigated and compared.
Highlights
Metal-organic frameworks (MOFs) [1], as a relatively new class of crystalline coordination polymers, have in the past decades become one of the fastest growing fields in chemistry, which is due to the significance both in academia and industry for their structural varie-ties and for their fascinating potential applications as functional crystalline materials, including gas storage, carbon dioxide capture and renewable catalysts [2-10]
The crystal structures and coordination modes of metal centers and sulfate ions, as well as the novel reaction mechanism and different conditions of lanthanide ions and 5-sulfosalicylic acid to form the series of lanthanide sulfate complexes, were discussed in detail
Metal-organic frameworks (MOFs) [1], as a relatively new class of crystalline coordination polymers, have in the past decades become one of the fastest growing fields in chemistry, which is due to the significance both in academia and industry for their structural varieties and for their fascinating potential applications as functional crystalline materials, including gas storage, carbon dioxide capture and renewable catalysts [2-10]
Summary
Metal-organic frameworks (MOFs) [1], as a relatively new class of crystalline coordination polymers, have in the past decades become one of the fastest growing fields in chemistry, which is due to the significance both in academia and industry for their structural varie-. Lanthanide-organic frameworks (LMOFs) possess more unique advantages because of the better optics and magnetism characters from the lanthanide themselves and more coordination numbers which is due to the larger radii of the lanthanide atoms [11-16]. A great number of examples about lanthanide-organic framework with rigid aromatic multicarboxylate have been reported, such as benzoic acid [34,35], 1,2-benzene dicarboxylic acid (o-H2BDC) [36], 1,3-benzene dicarboxylic acid (m-H2BDC) [37,38], 1,4benzene dicarboxylic acid (p-H2BDC) [39,40], benzene-1,3,5-tricarboxylic acid (H3BTC) [41], and 1,2,4,5benzenetetracarboxylic acid (H4BTEC) [42,43]. 5-sulfosalicylic acid, possessing three potential coordinating groups, -COOH, -SO3H and -OH, can act as the preferential ligand of the lanthanide complexes [48-51]. In our previous work, we selected 5-sulfosalicylic acid and at the same time chose dodecanedioic acid in synthesizing the rigid-flexible lanthanide coordination polymers. We used a reaction in situ to synthesize a series of the sulfato lanthanide complexes, Ln2(SO4)3(H2O) (Ln=Pr[1], Nd[2], Tb[3], Sm[4], Dy[5], Gd[7], Ho[8]), EuK(SO4)2 [6] (shown in Scheme 1)
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