Effect of Lanthanide Contraction on Crystal Structures of Three-Dimensional Lanthanide Based Metal–Organic Frameworks with Thiophene-2,5-Dicarboxylate and Oxalate

Abstract

Six three-dimensional (3D) lanthanide coordination polymers with formula [Ln(TDC)(ox)0.5(H2O)2]·(H2O) (1Ln) (Ln = Pr 1, Nd 2, Sm 3, Gd 4) and [Ln(TDC)(ox)0.5(H2O)2]·(H2O) (2Ln) (Ln = Dy 5, Er 6) have been synthesized by hydrothermal reactions of thiophene-2,5-dicarboxylate (TDC) and oxalate (ox) with corresponding lanthanide nitrate. X-ray crystal structure analyses reveal that 1Ln and 2Ln are isomers that may be produced by lanthanide contraction. Compounds 1–4 are isostructural and possess binodal (4,5)-connected 3D framework of tcj/hc topology with triangular channels along the [101] direction. Isostructural compounds 5 and 6 present trinodal (4,4,6)-connected 3D framework of sqc254 topology with rectangular channels along the b axis. The magnetic properties reveal that compound 2 has antiferromagnetic behavior, while compound 4 has ferromagnetic behavior. The luminescent property shows that compound 5 displays intense yellow luminescence and exhibits the typical Dy3+ ion emission. Furthermore, infrared (IR), thermogravimetric analyses (TGA), elemental analyses (EA), powder X-ray diffraction (PXRD), magnetic and luminescent properties of these compounds are also investigated.

Photoluminescence Properties of Lanthanide‐Organic Frameworks (LnOFs) with Thiophene‐2,5‐Dicarboxylate and Acetate

“…The Sm–O bond lengths range from 2.340(3) to 2.529(3) Å, and the O–Sm–O bond angle varies from 51.20(11) to 155.53(11)°. All of the bond lengths and angles in 5 are comparable with those reported values in Sm 3+ carboxylate compounds …”

N-(sulfoethyl) iminodiacetic acid-based lanthanide coordination polymers: Synthesis, magnetism and quantum Monte Carlo studies

“…Finally, the dimension of structure is also different: 2D for 1 and 4, 1D for 2 and 3. It is mentioned that other groups and we had reported the effect of lanthanide contraction on the structure of lanthanide-based coordination polymers [7][8][9][10][11][12][13][14][15][16][17]. Moreover, the flexibility SIDA 3 À ligand also affects the structure of 1-4.…”

“…So far, a great number of lanthanide coordination polymers with aesthetically interesting structures [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] have been prepared by selecting the appropriate ligands and controlling the reaction conditions. Nonetheless, owing to the variable and versatile coordination behavior of 4f metals and the effect of external physical or chemical stimuli on coordination reaction, the rational design and synthesis of lanthanide coordination polymers with desired structures still remains a great challenge [7][8][9][10][11][12][13][14][15][16][17][18]. Especially, lanthanide contraction usually plays an important role in the topological structure of lanthanide coordination polymers [7][8][9][10][11][12][13][14][15][16][17][18].…”

“…Nonetheless, owing to the variable and versatile coordination behavior of 4f metals and the effect of external physical or chemical stimuli on coordination reaction, the rational design and synthesis of lanthanide coordination polymers with desired structures still remains a great challenge [7][8][9][10][11][12][13][14][15][16][17][18]. Especially, lanthanide contraction usually plays an important role in the topological structure of lanthanide coordination polymers [7][8][9][10][11][12][13][14][15][16][17][18]. On the other hand, iminodiacetic acid (H 2 IDA), featuring unique chelate carboxyl and amido, had been widely applied to synthesize high lanthanide-transition metal (3d-4f) heterometallic clusters and coordination polymers [19][20][21][22][23][24], whereas corresponding studies with respect to its lanthanide coordination polymers are relative rare [25,26].…”

Tubular solids of lanthanide-doped polyoxometalates in micrometer-scale: synthesis and NIR-luminescent properties

“…The luminescent properties of lanthanide ions display advantages in that they absorb and emit light over narrow wavelength ranges with high quantum yields [7][8][9][10][11][12][13].…”