Multifunctional Luminescence Sensors Assembled with Lanthanide and a Cyclotriveratrylene‐Based Ligand

Abstract

By using a cyclotriveratrylene‐based ligand 5,12,19‐trimethoxy‐6,13,20‐tricarboxy‐methoxy‐cyclotriveratrylene (H3L), four lanthanide‐based compounds, Eu(L)(DMF)2 (1), Tb(L)(DMF)2 (2), Gd(L)(DMF)2 (3), and Yb(L)(DMF)(H2O) (4), have been constructed. Compounds 1–3 are isostructural and show charming two‐bowl interlocked chains linked by L3– anions and Ln3+ cations. The chains are further linked by C–H···π interactions to form two‐dimensional supramolecular layers, respectively. In 4, L3– anions bridge Yb3+ ions to yield a fascinating three‐dimensional framework. The compounds are characterized by IR and powder X‐ray diffraction. Their solid UV/Vis spectra and fluorescence properties are also studied. By fluorescence detection of metal cations, anions, and organic small molecules, compounds 1 and 2 exhibit high selectivity and sensitivity to Fe3+ ions, MnO4– anions, and nitromethane by quenching processes.

A Dual‐Responsive Luminescent Terbium(III) Chain for Selective Sensing of Fe3+ and MnO4– Ions

“…In addition, the LOD of 1 towards MnO 4 – is 1.43 μ m ( δ = 0.23 ppm). As compared with the known rare earth and/or transition metal ion‐based chemsensors, the of K sv value of 1 in water system is comparable with the complexes with different structures [ Ln (L 3 )(DMF) 2 ] ( Ln = Tb and Eu), [Pb 3 (BPDP) 1.5 (Hbdc) 3 ], and {[Ba 3 La 0.5 (μ 3 ‐L 4 ) 2.5 (H 2 O) 3 (DMF)] · (3DMF)} n , and is much smaller than those of the complexes [Tb(TBOT)(H 2 O)](H 2 O) 4 (DMF)(NMP) 0.5 , [Pb(BPDP)], and In(OH)(bpydc)‐Eu (Table ) . Since these known sensors with various structures are constructed from different metal ions and organic ligands, it can be concluded that the quench constant can be governed by various factors.…”

Three Coordination Polymers Based on Resorcin[4]arene as Effective Catalysts for the Knoevenagel Condensation Reaction and as Multifunctional Luminescent Sensors

“…The luminescent lifetimes are τ 1 =1.7798 ns (49.01%), τ 2 =6.1431 ns (50.99%) (χ 2 =1.006) for 1 , and τ 1 =1.7206 ns (64.93%), τ 2 =5.2109 ns (35.07%) (χ 2 =1.006) for 3 (Figure S8). Their short lifetimes should come from singlet emissions …”

Coordination polymers with embedded recognition sites: lessons from cyclotriveratrylene-type ligands

“…For example, the series of isostructural luminescent coordination polymers [M(L22)(DMF) 2 ], where M = Eu, Tb, Gd and L22 is a carboxylate-decorated CTV ligand, reported by Ma et al, exhibit an intra-cavity host-guest association between a lanthanidecoordinated DMF and L22 3− ligand. 25 That lanthanide also binds to the carboxylate groups of the same L22 3− ligand. which occurs without structural changes.…”

“…which occurs without structural changes. 25 A further example of a material with an intra-chain coordinated host-guest motif is found in {[Eu(L23)(DMF)(H 2 O)]•1.5(DMF)(H 2 O)} 18 which utilises a distinct carboxylate-decorated CTV ligand. The structure features a carboxylate-bridged Eu-dimer with terminal DMF and aquo ligands.…”

“…Pillararenes, crown ethers, cucurbiturils and cyclodextrins have also been employed. Our own work, [9][10][11][12][13][14][15][16][17][18][19][20][21] alongside that of other research groups, [22][23][24][25][26] has investigated the use of functionalised cyclotriveratrylenes (CTVs) as bridging ligands for coordination polymers. Cyclotriveratrylene (CTV) is a bowl-shaped molecular host with a tribenzo [a,d,g] cyclononatriene core.…”