Effective Mercury Sorption by Thiol-Laced Metal–Organic Frameworks: in Strong Acid and the Vapor Phase

• Published in: Journal of the American Chemical Society Vol. 135; no. 21; pp. 7795 - 7798
• Main Authors: Yee, Ka-Kit, Reimer, Nele, Liu, Jie, Cheng, Sum-Yin, Yiu, Shek-Man, Weber, Jens, Stock, Norbert, Xu, Zhengtao
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 29.05.2013
• Subjects: aluminum; aluminum chloride; coordination polymers; crystals; mercury; photoluminescence; sorption; thiols; vapors; zirconium
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/ja400212k

Free-standing, accessible thiol (−SH) functions have been installed in robust, porous coordination networks to provide wide-ranging reactivities and properties in the solid state. The frameworks were assembled by reacting ZrCl4 or AlCl3 with 2,5-dimercapto-1,4-benzenedicarboxylic acid (H2DMBD), which features the hard carboxyl and soft thiol functions. The resultant Zr-DMBD and Al-DMBD frameworks exhibit the UiO-66 and CAU-1 topologies, respectively, with the carboxyl bonded to the hard Zr(IV) or Al(III) center and the thiol groups decorating the pores. The thiol-laced Zr-DMBD crystals lower the Hg(II) concentration in water below 0.01 ppm and effectively take up Hg from the vapor phase. The Zr-DMBD solid also features a nearly white photoluminescence that is distinctly quenched after Hg uptake. The carboxyl/thiol combination thus illustrates the wider applicability of the hard-and-soft strategy for functional frameworks.