鈥淐lick鈥?on MOFs: A Versatile Tool for the Multimodal Derivatization of N3-Decorated Metal Organic Frameworks
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- 作者：Giulia Tuci ; Andrea Rossin ; Xiaoying Xu ; Marco Ranocchiari ; Jeroen A. van Bokhoven ; Lapo Luconi ; Ilse Manet ; Manuela Melucci ; Giuliano Giambastiani
- 刊名：Chemistry of Materials
- 出版年：2013
- 出版时间：June 11, 2013
- 年：2013
- 卷：25
- 期：11
- 页码：2297-2308
- 全文大小：814K
- 年卷期：v.25,no.11(June 11, 2013)
- ISSN：1520-5002
文摘
Postsynthetic modification (PSM) has been exploited for the preparation of two novel N3-decorated MOFs, namely, UMCM-1-N3 [Zn4O(N3tpa)(btb)4/3; N3tpa2鈥?/sup> = 2-azidoterephthalate; btb3鈥?/sup> = 4,4鈥?4鈥?benzene-1,3,5-triyl-tribenzoate] and MIXMOF-5-N3 [Zn4O(N3tpa)0.4(tpa)2.6; tpa2鈥?/sup> = terephthalate], featured by both different azido functional group content and crystalline structure. Subsequently, the as-synthesized materials were further transformed through an efficient and versatile approach capable of imparting multimodality to these porous organic鈥搃norganic polymers. Cu-mediated acetylene鈥揳zide coupling (CuAAC; 鈥渃lick鈥?reaction) has been performed in a single step, under optimized conditions, with complete azido 鈫?triazole conversion using either single acetylene derivatives or mixtures of reactive terminal alkynes in variable molar fractions to give homo- and heteroderivatized MOFs. An accurate control of the relative percentages of the functional groups in the final heterofunctionalized materials is conveniently achieved through a fine-tuning of the starting acetylene mixtures molar ratio. All MOFs derivatives have been characterized through thermogravimetric analysis coupled with MS analysis of volatiles (TG-MS), powder X-ray diffraction (PXRD), FT-IR spectroscopy, and 1H NMR spectroscopy of the digested functionalized samples. Fluorescence studies on properly labeled (dye-functionalized) MOFs have been used for the first time to assess the statistical distribution of the 鈥渞eactive probe鈥?throughout the bulk material.