A new pair of multifunctional Zn(II)-Yb(III) complex enantiomers based on a chiral amine-phenol ligand, [YbZn2(SS/RR-L)2(H2O)4](ClO4)3•5H2O (S-1 and R-1) [H2L = ((SS/RR)-cyclohexane-1,2-diylbis(azanediyl))-bis(methylene))-bis(2-methoxyphenol))], were synthesized and structurally characterized. In S-1 and R-1,...
Crystalline molecular materials exhibiting both proton conduction and single-molecule magnet (SMM) behaviors would offer a great opportunity for applications in fuel cells, molecular spintronics and high-density data storage technologies. However,...
Luminescent metal−organic frameworks (MOFs) coupled with proton conduction offer wide applications in clean energy and luminescence sensors. High stability and remarkable proton conductivity and sensing are requisites for practical applications. Specifically, high thermal and chemical stabilities under harsh conditions are important but challenging to achieve. Herein, an ultra-stable Cu(I)-tetrazolate MOF, NaCu 3 (mtz) 4 (1, mtz = 5-methyltetrazolate), was prepared. It possesses a 3D framework with 1D channels and exhibits outstanding thermal and chemical stabilities under various conditions, including water, organic solvents, and acidic and basic solutions of wide pH range. The compound exhibits strong green emissions, which can be ascribed to metal-toligand charge transfer, and selective fluorescence sensing for pollutant nitrobenzene. Moreover, compound 1 presents a high proton conductivity of over 10 −2 S cm −1 at 70 °C and 100% relative humidity. In 1, abundant uncoordinated nitrogen atoms on the pore walls act as H-bonding acceptors to achieve its high proton conductivity under waterassisted conditions. The compound is an unprecedented water-dependent proton conductor of the tetrazole-based MOF, providing a new avenue to design robust and high-performance proton-conductive MOFs.
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.
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