ic400770j_si_001.pdf (1.06 MB)
Highly Selective Luminescent Sensing of Fluoride and Organic Small-Molecule Pollutants Based on Novel Lanthanide Metal–Organic Frameworks
journal contribution
posted on 2013-07-15, 00:00 authored by Jing-Min Zhou, Wei Shi, Na Xu, Peng ChengTwo novel isostructural lanthanide
metal–organic frameworks (Ln-MOFs), [Ln2(BPDC)(BDC)2(H2O)2]n (Ln = Eu (1) and Tb (2)), have been successfully
synthesized via a mixed ligand approach using 2,2′-bipyridine-3,3′-dicarboxylic
acid (H2BPDC) and 1,4-benzenedicarboxylic acid (H2BDC) under hydrothermal conditions. Structural analysis shows that
two lanthanide ions are 4-fold linked by two κ1-κ1-μ2 carboxylates from BDC2– and the other two κ2-κ1-μ2 carboxylates from BPDC2– to form a binuclear
core. The binuclear units are further connected by BDC2– and BPDC2– to build a three-dimensional framework
possessing tfz-d topology with the short (Schläfli)
vertex symbol {43}2{46·618·84}. Moreover, isostructural doped Ln-MOFs
[Eu2xTb2(1–x)(BPDC)(BDC)2(H2O)2]n (x = 0.1 (1a), 0.3
(1b), 0.5 (1c), 0.7 (1d), and
0.9 (1e)) were also successfully synthesized. Thermal
gravimetric analyses (TGA) reveal high thermal stability of these
Ln-MOFs. Luminescent measurements indicate that the characteristic
sharp emission bands of Eu3+ and Tb3+ ions are
simultaneously observed in 1a–e.
Further luminescent studies reveal that 1, 2, and 1a not only display a high-sensitivity sensing
function with respect to fluoride but also exhibit significant solvent-dependent
luminescent response to small-molecule pollutants, such as formaldehyde,
acetonitrile, and acetone.