Postsynthetic Modification: A Versatile Approach Toward Multifunctional Metal-Organic Frameworks

被引:195
作者
Garibay, Sergio J. [1 ]
Wang, Zhenqiang [1 ]
Tanabe, Kristine K. [1 ]
Cohen, Seth M. [1 ]
机构
[1] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA
关键词
ZEOLITIC IMIDAZOLATE FRAMEWORKS; INFINITE POLYMERIC FRAMEWORKS; COORDINATION POLYMERS; HYDROGEN STORAGE; COVALENT MODIFICATION; SURFACE MODIFICATION; RETICULAR SYNTHESIS; CARBON-DIOXIDE; DRUG-DELIVERY; POROUS SOLIDS;
D O I
10.1021/ic900796n
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
An isoreticular metal-organic framework (IRMOF-3) containing 2-amino-1,4-benzenedicarboxylic acid (NH2-BDC) as a building block is shown to undergo chemical modification with a diverse series of anhydrides and isocyanates. The modification of IRMOF-3 by these reagents has been evidenced by using a variety of methods, including NMR and electrospray ionization mass spectrometry, and the structural integrity of the modified MOFs has been confirmed by thermogravimetric analysis, powder X-ray diffraction, and gas sorption analysis. The results show that a variety of functional groups can be introduced onto the MOF including amines, carboxylic acids, and chiral groups. Furthermore, it is shown that tert-butyl-based asymmetric anhydrides can be used to selectively deliver chemical payloads to the IRMOF. Finally, the results demonstrate that at least four different chemical modifications can be performed on IRMOF-3 and that the reaction conditions can be modulated to control the relative abundance of each group. The findings presented here demonstrate several important features of postsynthetic modification on IRMOF-3, including (1) facile introduction of a wide range of functional groups using simple reagents (e.g., anhydrides and isocyanates), (2) the introduction of multiple (as many as four different) substituents into the MOF lattice, and (3) control over reaction conditions to preserve the crystallinity and microporosity of the resultant MOFs. The findings clearly illustrate that postsynthetic modification represents a powerful means to access new MOF compounds with unprecedented chemical complexity, which may serve as the basis of multifunctional materials.
引用
收藏
页码:7341 / 7349
页数:9
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