Crystal Engineering with the New Linker Tolanedisulfonic Acid (H₂TDS): Helical Chains in Zn(TDS)(DMA)₃, Linear Chains in Zn(TDS)(NMP)₃, and Complex Anions in [HDMA]₂[Zn(TDS)₂(DMA)₃](DMA)₂

Abstract

Reaction of 4,4'-tolanedisulfonic acid, H2 TDS, with zinc hydroxide in dimethylacetamide, DMA, under solvothermal conditions led to the coordination polymer Zn(TDS)(DMA)3 (I). In the crystal structure [trigonal, P32 21, Z=3, a=1175.0(1) pm, c=1949.5(1) pm, R1 ; wR2 (Io > 2σ(Io ))=0.0393; 0.0921] the disulfonate anions linked the Zn(2+) ions into helical chains according to ∞ (1) [Zn(DMA)3/1 (TDS)2/2 ] (I) causing the chirality of the compound. By using higher concentrations of H2 TDS in the starting mixture the compound [HDMA]2 [Zn(TDS)2 (DMA)3 ](DMA)2 (II) was formed. The structure [monoclinic, Cc, Z=4, a=1201.5(1) pm, b=1996.0(1) pm, c=2749.2(2) pm, β=101.897(2)°, R1 ; wR2 (Io > 2σ(Io ))=0.0699; 0.2017] displayed the complex anion [Zn(TDS)2 (DMA)3 ](2-) which was a perfect cut-off of the helical chain in I. Charge compensation was achieved by protonated DMA molecules. If N-methylpyrrolidone, NMP, was chosen as a solvent, the sulfonate Zn(TDS)(NMP)3 (III) [monoclinic, I2/a, Z=4, a=1575.7(1) pm, b=1077.3(1) pm, c=1870.0(1) pm, β=101.189(9)°, R1 ; wR2 (Io > 2σ(Io ))=0.0563; 0.1320] was obtained. Similarly to the findings for I, the formation of chains according to ∞ (1) [Zn(NMP)3/1 (TDS)2/2 ] was observed. However, due to the more bulky NMP molecules these chains were no longer helical but straight instead.

Tunable white light emission of Eu,Tb,Zn-containing copolymers by RAFT polymerization

“…In recent years, europium(III) organic complexes used as the red phosphor [21][22][23][24] in the fabrication of white LEDs have been reported because of their wide excitation band, high internal quantum yield, and good color purity. [25][26][27] In particular, most studies are focused on zinc(II) complexes to obtain blue light, 28,29 since they are capable of replacing beryllium(II) complexes that could be of harm to the environment.…”

Tunable white light emission of a large area film-forming macromolecular complex with a high color rendering index

“…Among the numerous kinds of phosphors, assemblies of lanthanide(Ш)-containing complexes have attracted considerable attentions for their effective and characteristic luminescence, with generally chosen red (Eu 3+ , Pr 3+ , Sm 3+ ), green (Tb 3+ , Er 3+ ), and blue (Dy 3+ , Be 2+ , Ce 3+ ) emissive ions [8][9][10][11][12]. What is worth noting is that most studies have focused on zinc(II) complexes [13] in the research field of blue light emission to replace beryllium(II) complexes, as the latter is too toxic to be applied in practice. Afterwards, small molecular complexes were introduced in the polymer matrix to avoid intrinsic shortcomings such as poor film-forming property in the process of preparation [14].…”