Angew Chem Int Ed Engl. 2014 Mar 10;53(11):2852-6. doi: 10.1002/anie.201309295.
Recently, the use of mixtures of organic-building-block linkers has given chemists an additional degree of freedom for engineering metal-organic frameworks (MOFs) with specific properties; however, the poor characterization of the chemical complexity of such MixMOF structures by conventional techniques hinders the verification of rational design. Herein, we describe the application of a technique known as photothermal induced resonance to individual MixMOF microcrystals to elucidate their chemical composition with nanoscale resolution. Results show that MixMOFs isoreticular to In-MIL-68, obtained either directly from solution or by postsynthetic linker exchange, are homogeneous down to approximately 100 nm. Additionally, we report a novel in situ process that enables the engineering of anisotropic domains in MOF crystals with submicron linker-concentration gradients.
最近,使用有机砌块链接剂的混合物为化学家提供了额外的自由度,可以用特定的属性来设计金属-有机骨架(MOF);然而,传统技术对这种 MixMOF 结构化学复杂性的描述不足,阻碍了对合理设计的验证。在此,我们描述了一种称为光热诱导共振的技术在单个 MixMOF 微晶体上的应用,以纳米级分辨率阐明其化学成分。结果表明,与 In-MIL-68 等结构的 MixMOF 无论是直接从溶液中获得还是通过后合成的链接交换获得,在大约 100nm 以下都是均匀的。此外,我们还报告了一种新的原位过程,该过程可以在亚微米级的链接浓度梯度下对 MOF 晶体进行各向异性域的工程设计。