Bismuth(iii)-thiophenedicarboxylates as host frameworks for lanthanide ions: synthesis, structural characterization, and photoluminescent behavior

Abstract

Three bismuth-2,5-thiophenedicarboxylates (Bi-TDC) and two europium-2,5-thiophenedicarboxylates (Eu-TDC) were synthesized under ambient conditions. The structures were determined through single crystal X-ray diffraction, and three of the phases were further characterized by powder X-ray diffraction, Raman spectroscopy, and thermogravimetric analysis. Reactions of bismuth nitrate, 2,5-thiophenedicarboxylate, and pyridine in an acidic solution of acetic acid and ethanol yield Hpy[Bi(TDC)2(H2O)]·1.5H2O (1), whereas reactions in a water/ethanol mixture produce a minor phase, [Hpy]3[Bi2(TDC)4(HTDC)(H2O)]·xH2O (2) along with a major product, (Hpy)2[Bi(TDC)2(HTDC)]·0.36H2O (3). The structures of 1-3 are all built from anionic Bi-TDC chains that are further bridged through additional TDC linkages into interpenetrated 2D sheets. Addition of an aqueous lanthanide solution to the reaction mixtures that yielded 1 and 2-3 resulted in the formation of doped phases, Hpy[Bi1-xLnx(TDC)2(H2O)]·1.5H2O (Bi1-xLnx-1), where Ln = Nd, Sm, Eu, Tb, Dy, and Yb, and (Hpy)2[Bi0.99Eu0.01 (TDC)2(HTDC)]·0.36H2O (Bi0.99Eu0.01-3). Using europium nitrate rather than the bismuth precursor resulted in the formation of two homometallic europium based phases, [Eu(TDC)(NO3)(H2O)]n (4) and [Eu2(TDC)3(H2O)9]·5H2O (5), which adopt an extended 3D network and an interpenetrated 2D structure, respectively. Photophysical measurements were carried out for 1 and the lanthanide containing phases and quantum yield and lifetime values were determined for the visible light emitters. Herein, the structural chemistry, spectroscopic properties, and luminescence of the bismuth phases, their lanthanide doped analogs, and the europium compounds are presented.

Synthesis and photoluminescence of three bismuth(iii)-organic compounds bearing heterocyclic N-donor ligands

“…42 Interestingly, the chlorobismuth dimer is accessible using terpy as a capping ligand, possibly owing to the increased denticity and ability of terpy to better saturate the metal coordination sphere. Furthermore, it is of note that while the structure of 1 exhibits a coordination environment consistent with the presence of a stereochemically active lone pair, as evidenced by the distorted metal coordination geometry, apparent open face, and elongation of Bi⋯Cl interactions, 23,26,69 little evidence of lone pair activity about the Bi centers is present in 2 and 3.…”

“…Recently, though, bismuth-based compounds have attracted increasing attention due, in part, to their unique photoluminescence behaviour. [12][13][14][15][16][17][18][19][20][21][22][23] Trivalent bismuth has a [Xe]4f 14 5d 10 6s 2 electron configuration and possesses lone pair electrons (6s 2 ) with variable stereochemical activity. This results in a flexible coordination environment ranging from a hemidirected to holodirected coordination sphere, a range of coordination numbers, and thus, the potential for novel structuretypes.…”

“…This results in a flexible coordination environment ranging from a hemidirected to holodirected coordination sphere, a range of coordination numbers, and thus, the potential for novel structuretypes. 14,[21][22][23][24][25][26][27] Yet, such structural diversity combined with the limited solubility and hydrolytic propensity of many Bi salt starting materials can provide significant challenges for controlled synthesis and structure prediction. As such, developing fundamental knowledge of the synthesis and structural chemistry of bismuth-organic-based phases is not only crucial for overcoming such challenges but also can provide key insight into the role that structural features have on materials properties such as luminescence.…”

Structure–Property Relationships in Photoluminescent Bismuth Halide Organic Hybrid Materials

“…All other synthetic conditions were maintained as described for the homometallic analog, 3A-Cl. Note that while previous work has shown that lanthanides often incorporate into Bi host materials at much lower doping percentages than those used in the synthesis, 52,56 due to phase impurities for several of the doped samples, the reported Eu doping percentages correspond to the amount of Eu 3+ relative to Bi 3+ used in the synthesis. An increase in Eu doping percentage with increased synthetic loading is consistent with an increase in Eu emission across the doped samples from 0.1 to 1% Eu doping.…”

Bi(iii) MOFs: syntheses, structures and applications

“…Within the range of the blue-green spectrum, K1 and K2 show spectral differences, which may be related to the different coordination environments. Adcock and coworkers have investigated the fluorescence properties of the lanthanide-ion doped compounds of Hpy[Bi (TDC) 2 (H 2 O)]•1.5H 2 O (L1) and (Hpy) 2 [Bi(TDC) 2 (HTDC)]•0.36H 2 O (L3) 85. The specific operation method is as follows:Hpy [Bi 1−x ln x (TDC) 2 (H 2 O)]•1.5H 2 O (Bi 1−x ln x -L1) (Ln =Nd, Sm, Eu, Tb, Dy, Yb) and [Bi 0.99 Eu 0.01 (TDC) 2 (HTDC)(Hpy) 2 ] (Bi 0.99 Eu 0.01 -L3) were prepared by adding rare earth nitrate solution in the process of L1, L3 synthesis.…”