Lanthanide coordination polymers based on designed bifunctional 2-(2,2′:6′,2″-terpyridin-4′-yl)benzenesulfonate ligand: syntheses, structural diversity and highly tunable emission

Abstract

Seven novel lanthanide coordination polymers, [Eu(STP)(glu)]n (1), [Ln4(STP)2(glu)5]n·4nH2O [Ln = Er (2), Yb (3)], [Ln(STP)(1,3‐bdc)]n·0.5nH2O [Ln = Tb (4), Yb (5)], and [Ln(STP)(1,2‐bdc)]n [Ln = Eu (6), Tb (7)] [NaSTP = sodium 2‐(2,2′:6′,2″‐terpyridin‐4′‐yl)benzenesulfonate, H2glu = glutaric acid, H2(1,3‐bdc) = benzene‐1,3‐dicarboxylic acid, H2(1,2‐bdc) = benzene‐1,2‐dicarboxylic acid], have been prepared under hydrothermal conditions and characterized by elemental analysis, IR and single‐crystal X‐ray diffraction. Compound (1) possesses a 2D layered structure based on 1D chains with STP− and glu2− anions acting as bridges. Compounds (2) and (3) are isomorphous and show a rare 3D tcj/hc net with a tetranuclear Ln3+ unit regarded as a seven‐connected node and a glu2− anion serving as a three‐connected node. Compounds (4) and (5) are isomorphous and exhibit six‐connected pcu nets by denoting binuclear units to six‐connected nodes. Compounds (6) and (7) display 3D 3,5T1 nets with (1,2‐bdc)2− anions and dimetallic units serving as three‐ and five‐connected nodes, respectively. The Eu compounds (1) and (6) demonstrate typically red emission, while the Tb compounds (4) and (7) exhibit characteristic green emission. The emission spectra of heteronuclear compounds [EuxTb1−x(STP)(1,2‐bdc)]n (0 ≤ x ≤ 1) as efficient luminescent tags were investigated. The intermetallic energy transfer of Tb to Eu was also evaluated.

Two-Dimensional Metal-Organic Framework Materials: Synthesis, Structures, Properties and Applications

“…via in situ co-doping of lanthanide ions into [Bi 2 Cl 6 (pz) 4 ] to form [Bi (2– x ) ­Ln x ­Cl 6 ­(pz)­ 4 ] (Ln = Sm, Eu, Tb, and Dy), which showed lanthanide-based emission at room temperature, but on cooling to 77 K, bismuth–pyrazine MLCT related bluish-white phosphorescence at 495 nm was revealed . Several other examples based on Eu 3+ and Tb 3+ metal centers exhibiting red and green emission, respectively, are also noted. − …”

A new praseodymium-based coordination polymers with 1,10-phenantroline and glutarate ligands: Synthesis, crystal structure and luminescent properties

“…The use of bulky ligands prevents solvent molecules coordination. Rigid organic ligands such as 1,10-phenantroline have proved their efficiency [19][20][21][22][23][24]. However, these bulky ligands often lead to 0D complexes.…”