Solvothermal syntheses, crystal structures and luminescence properties of three new lanthanide sulfate fluorides

Abstract

Three novel lanthanide sulfate fluorides of formulae [C(4)H(16)N(3)](6)[Sm(4)F(2)(SO(4))(14)] 1 and LnFSO(4).H(2)O (Ln = Tb 2; Nd 3) have been synthesized solvothermally and structurally characterized by single-crystal X-ray diffraction, IR, TGA, SEM, and ICP. Single crystal X-ray diffraction reveals that compound 1 crystallizes in the triclinic crystal system, with space group P-1 and cell dimensions: a = 11.1988(9), b = 11.4073(9), c = 16.2666(13) A, alpha = 89.9010(10) degrees, beta = 82.4060(10) degrees, gamma = 67.7570(10) degrees, V = 1903.9(3) A(3), Z = 1. Both compounds 2 and 3 crystallize in the monoclinic crystal system, with the space group P2(1)/n and cell dimensions: a = 5.0014(7), b = 7.3769(11), c = 11.6508(17) A, beta = 96.692(2) degrees, V = 426.93(11) A(3), Z = 4 for 3; a = 4.9948(5), b = 7.3684(7), c = 11.6366(12) A, beta = 96.6720(10) degrees, V = 425.37(7) A(3), Z = 4 for 3. The structure of 1 consists of a novel isolated large Z-type heteropolyanion [Sm(4)F(2)(SO(4))(14)](18-) and full protonated organic amine cations. The chains are held together by hydrogen bond interactions involving the hydrogen of the amine and the framework oxygen. The compounds 2 and 3 are isostructural and their structures feature a three-dimensional network constructed from the left-handed and the right-handed helical channels which are connected by SO(4)(2-) groups using 6-membered rings and 4-membered rings.

Solvothermal Synthesis, Crystal Structure, and Luminescent Properties of Three Heterometallic Lanthanide‐Transition‐Metal Frameworks Constructed from Three Types of CuBr Motifs

“…The emission spectrum exhibits the characteristic transition of Sm III ion. Compound 2 shows three emission bands at 560, 598, and 646, arising from the 4 G 5/2 → 6 H J ( J = 5/2, 7/2, 9/2) with the 4 G 5/2 → 6 H 7/2 emission as the dominant band, which is in agreement with those reported Sm III compounds . The absence of the IN – ligand emission in the fluorescence spectra indicates an efficient energy transfer from the IN – ligands to the central lanthanide ions, which can enhance the fluorescence efficiency, but also effectively reduces the loss of energy by radiationless thermal vibrations and increases the rigidity of molecule.…”

“…The bond lengths of Gd–O range from 2.260(3) to 2.779(4) Å, whereas the bond angles of O–Gd–O are between 64.65(10) and 154.56(11)°. All the bond lengths and bond angles are in accordance to the reported literature . Scheme a and b shows the coordination modes of IN – ligands in compound 1 : it is clearly showing that there exist two kinds of coordination modes in compound 1 , all the IN – ligands coordinate to Gd1 ions in a μ 3 ‐η 1 :η 1 mode, while one of the IN – ligands coordinates to Gd2 ions in a μ 1 ‐η 1 mode as a terminal ligand and the others are similar to Gd1.…”

Hydrothermal synthesis and characterization of a Na+ templated new 3-D lanthanum sulfate Na[C6H14N2][La3(SO4)6(H2O)3] constructed from La–O–S tubes and cubic cages

“…As shown in Fig. 1 [4,25,27,30,31]. The O-S-O angles are within the expected range of tetrahedral geometry.…”

Solvothermal and hydrothermal processes: the main physico-chemical factors involved and new trends

“…-with a particular composition (for example the extension from oxides systems to fluorides [132], sulphides [133,134], sulphate-fluorides [135], nitrides [136,137], hybrids [138], carbon-systems [139], metallic systems [140], metalorganic frameworks [141], etc. ); -with the synthesis of specific structures, such as perovskite or pyrochlore, in mild conditions [142]; -with some specific characteristics in size but mainly in morphology such as nanotubes [127], fibrous systems [143], nano-composites [144]; -with a specific application (as nanophosphors) [145,146], -nano-composites associating different classes of materials (such as carbon and oxides) [147].…”