ABSTRACT
Multifunctional materials with a coexistence of proton conduction properties, single-molecule magnet (SMM) behaviors and magneto-optical Faraday effects have rarely been reported. Herein, a new pair of Cu(II)-Dy(III) enantiomers, [DyCu2(RR/SS-H2L)2(H2O)4(NO3)2]·(NO3)·(H2O) (R-1 and S-1) (H4L = [RR/SS] -N,N'-bis [3-hydroxysalicylidene] -1,2-cyclohexanediamine), has been designed and prepared using homochiral Schiff-base ligands. R-1 and S-1 contain linear Cu(II)-Dy(III)-Cu(II) trinuclear units and possess 1D stacking channels within their supramolecular networks. R-1 and S-1 display chiral optical activity and strong magneto-optical Faraday effects. Moreover, R-1 shows a zero-field SMM behavior. In addition, R-1 demonstrates humidity- and temperature-dependent proton conductivity with optimal values of 1.34 × 10-4 S·cm-1 under 50 °C and 98% relative humidity (RH), which is related to a 1D extended H-bonded chain constructed by water molecules, nitrate and phenol groups of the RR-H2L ligand.
ABSTRACT
A new Dy-based complex, [Dy2(phen)4(PAA)4](ClO4)2 (1), was obtained by using 4-hydroxyphenyl acetate (HPAA) as a ligand and 1,10-phenanthroline as an auxiliary ligand. Complex 1 shows a dinuclear structure and a 2D supramolecular layer constructed by π-π stacking interactions. The complex displays a characteristic Dy(III) emission. Moreover, magnetic susceptibility measurements revealed that 1 exhibits a single-molecule magnet (SMM) behavior. In addition, it also shows a proton conductivity of 1.08 × 10-5 S cm-1 under 353 K and 100% relative humidity conditions, which is mainly assigned to H-bonded networks formed by the undeprotonated and uncoordinated phenolic groups of HPAA ligands and guest water molecules. Remarkably, 1 is the first example of a dinuclear complex showing photoluminescence, SMM behavior, and proton conduction.
ABSTRACT
Four complexes from lanthanides, 3-pyridylacetate, and 1,10-phenanthroline, formulated as [Ln2(3-PAA)2(µ-Cl)2(phen)4](ClO4)2 [Ln = Gd(1), Dy(2), Eu(3), Tb(4), 3-PAA = 3-pyridylacetic acid, phen = 1,10-phenanthroline], were obtained. The four compounds were characterized by IR spectra, thermogravimetric analyses, powder X-ray diffraction, and single-crystal X-ray diffraction. Compounds 1-4 are isomorphous, and they have a dinuclear structure. Magnetic studies reveal that 1 shows the magnetocaloric effect with -ΔS m max = 19.03 J kg-1 K-1 at 2 K for ΔH = 5 T, and 2 displays a field-induced single-molecule magnet with U eff = 19.02 K. The photoluminescent spectra of 3 and 4 exhibit strong characteristic emission, which demonstrate that the ligand-to-EuIII/TbIII energy transfer is efficient.
ABSTRACT
Three types of lanthanide complexes based on the tetrazole-1-acetic acid ligand and the 2,2'-bipyridine coligand were prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analyses; the formulas of these complexes are [Ln2(1-tza)4(NO3)2(2,2'-bipy)2] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5)), [Dy2(1-tza)4Cl2(2,2'-bipy)2] (6), and [Yb2(1-tza)4(NO3)2(2,2'-bipy)2] (7) (1-tza = tetrazole-1-acetate and 2,2'-bipy = 2,2'-bipyridine). They are dinuclear complexes possessing similar structures but different lanthanide(III) ion coordination geometries because of the distinction of peripheral anions (such as NO3(-) and Cl(-)) and the effect of lanthanide contraction. The variable-temperature magnetic susceptibilities of 1-6 were measured. Both Dy(III) complexes (5 and 6) display field-induced single-molecule magnet behaviors. Ab initio calculations revealed that the Dy(III) complex 6 possesses a more anisotropic Dy(III) ion in comparison to that in 5. The room-temperature photoluminescence spectra of Sm(III) (1), Eu(III) (2), Tb(III) (4), and Dy(III) (5 and 6) complexes exhibit strong characteristic emissions in the visible region, whereas the Yb(III) (7) complex shows near-infrared (NIR) luminescence.
