A thiol-functionalized zirconium metal-organic cage for the effective removal of Hg2+ from aqueous solution.

The mercury ions in waste water have threatened public health and environmental protection. In this sense, novel materials with outstanding performances for removal of Hg2+ are imperative. Herein, we demonstrate a thiol-functionalized zirconium metal-organic cage (MOC-(SH)2) with excellent dispersion displays ideal properties for Hg2+ capture. MOC-(SH)2 exhibits the ability of removing Hg2+ in aqueous solutions with a capacity of 335.9 mgHg2+/gMOC-(SH)2, which surpasses that of classical Zr-based metal-organic framework Uio-66-(SH)2 by 1.89 folds. The higher loading capacity of MOC-(SH)2 is probably owing to the excellent dispersion of the discrete cage, which makes the accessibility of binding sites (thiol) easier. Additionally, 99.6% of Hg2+ can be effectively captured by MOC-(SH)2 with the concentration decreased from 5 to 0.02 ppm reaching the permissible limit for Hg2+, outperforming the performance of Uio-66-(SH)2. The excellent absorption property of MOC-(SH)2 is also achieved in terms of superior selectivity under the presence of competitive metal ions. Meanwhile, the regenerated MOC-(SH)2 can be reused without apparent loss of Hg2+ loading capacity. UV-vis absorption spectra, IR spectra and emission spectra further verified the strong chemical affinity between Hg2+ and the thiol of MOC-(SH)2. The study lays the groundwork for using Zr-MOCs in the removal of toxic metal ions and environmental sustainability.

Metal ions doped into merocyanine form of coumarin derivatives: nonlinear optical molecular switches.

In the present study, DFT calculations are carried out on domestically designed 7-methyl-2-phenyl-5'H-spiro[chromene-4,2'-chromeno[3,4-e][1,3]oxazin]-5'-one spiropyran and merocyanine derivatives to recognize alkali and alkaline earth metal ions. Detection of these metal ions can be attained by exploiting the variation of the second-order nonlinear optical properties. Merocyanine forms of these derivatives exhibit the ability to complex with different metal ions (Li+, Na+, K+, and Ca2+), which is associated with large contrasts in the hyper-Rayleigh scattering (HRS) response as a function of metal size and charge. Interestingly, in this study, Mero-Li+ shows significant nonlinear optical response with dynamic HRS first hyperpolarizability amounting to 7607 a.u., which is about nine times higher than its corresponding spiro form (846 a.u.) at the CAM-B3LYP/6-311G* level of theory. The present investigation clarifies the effect of metal nature on the enhancement of the first hyperpolarizability between the closed and open forms of the studied coumarin derivatives. Graphical abstract The coumarin-based compound 3 demonstrate the higher second-order NLO responses as a function of metal cation size and charges. Complexation of smaller alkali metal ions leads to the formation of stronger metal-ligand bonds, larger geometrical relaxations and significant enhancement of the HRS first hyperpolarizabilities. This present investigation elucidates the effect of metal nature on the enhancement of the first hyperpolarizability between the closed and open forms of studied coumarin derivatives.