Reactions of lanthanide(III) nitrates with multi-donor carboxylate ligand in the presence of oxalate anion afforded four new lanthanide coordination polymers with three dimensional (3D) frameworks, namely, {[Ln2(DPPA)2(μ2-C2O4)(H2O)2]·2H2O}n (Ln = Nd (1), Sm (2)) and [Ln2(HDPPA)2(DPPA)2]n (Ln = Tb (3), Yb (4)), (H3DPPA = 3-(4-hydroxyl pyridinium-1-yl) phthalic acid and H2C2O4 = oxalic acid). Compounds 1 and 2 are isostructural and isomorphous, featuring oxalate pillared binodal (4,5)-connected porous 3D framework with intersected 1D channels, in which the coordinated and lattice waters are accommodated. The complexes 3 and 4 are also isostructural, but featuring a (4,6)-connected 3D network based on a rectangular window composed of {Ln(HDPPA)}(+) extended anion chains, further interlinked by DPPA. The Tb(III) analogue exhibits intense characteristic green photoluminescence employing DPPA as an antenna. While Sm(III) compound 2 mainly involves ligand-to-ligand charge transfer. Variable-temperature susceptibility analyses of complexes 1 (Nd), 2 (Sm) and 3 (Tb) revealed that depopulation of the Stark levels together with weak antiferromagnetic interactions between the lanthanide ions lead to a continuous decrease in χ(M)T when the samples are cooled from 300 to 2 K.
Source of materialAm ixture of ZnO (0.5 mmol), 1,10-phenanthroline (phen, 0.5 mmol), 3-animo-4-chlorobenzenesulphonic acid (1.0 mmol) in H 2O(20 ml) was sealed into a25mlTeflon-lined stainless steel reactor and heated at 443 Kfor 1d.The reactor was then cooled slowly to room temperature and the solution was filtered. Red block-shaped crystals were obtained from the filtrate after several days at room temperature.
DiscussionThe design and construction of metal-organic coordination polymers is of current interest in the fields of supramolecular chemistry and crystal engineering. Major reasons for this interest stem from their intriguing variety of topologies and structural diversity, such as helixes and diamondoid nets, and from their potential applications as functional materials. So far, most of these materials are constructed by various rigid organic bidentate ligands containing pyridine rings, dicarboxylate, phosphonate, and sulfonate as spacers and metal cores as connectors [1][2][3][4][5][6]. 3-amino-4-chlorobenzenesulphonic acid is versatile coordinating ligands and it can act not only as hydrogen-bond aceptor but also as hydrogen-bond donor.In the title crystal structure, there are two 3-amino-4-chlorobenzenesulphonate anions, one Zn(II) ion, two phen, two coordinated water and two lattice water molecules in the asymmetric unit. Zn ion is six-cooridnated by two water oxygen atoms and four Natoms from two phen, forming adistorted octahedron. The bond angles around central Zn ion range from 77.38 (8)
C 22 H 32 N4O 13 S 2 Zn, triclinic, P¯ (no. 2), a = 9.496(1) Å,
CCDC no.: 1267/4297Source of material 4,4′-Diamino-1,1′-biphenyl-2,2′-disulfonic acid (0.25 mmol, 86 mg) was added with constant stirring to suspension of ZnO (0.25 mmol, 20 mg) in 10 mL of deionized water. Then the 5 mL ethanol solution of 4,4′-bipyridine (0.1 mmol, 15.6 mg) was added to the aforementioned solution
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