Bajpai Alankriti, Chandrasekhar Pujari, Govardhan Savitha, Banerjee Rahul, Moorthy Jarugu Narasimha
Department of Chemistry, Indian Institute of Technology, Kanpur-208016 (India), Fax: (+91) 512-2597436.
Chemistry. 2015 Feb 9;21(7):2759-65. doi: 10.1002/chem.201406098. Epub 2014 Dec 22.
The metal ions in a neutral Zn-MOF constructed from tritopic triacid H3 L with inherent concave features, rigid core, and peripheral flexibility are found to exist in two distinct SBUs, that is, 0D and 1D. This has allowed site-selective postsynthetic metal exchange (PSME) to be investigated and reactivities of the metal ions in two different environments in coordination polymers to be contrasted for the first time. Site-selective transmetalation of Zn ions in the discrete environment is shown to occur in a single crystal-to-single crystal (SCSC) fashion, with metal ions such as Fe(3+) , Ru(3+) , Cu(2+) , Co(2+) , etc., whereas those that are part of 1D SBU sustain structural integrity, leading to novel bimetallic MOFs, which are inaccessible by conventional approaches. To the best of our knowledge, site-selective postsynthetic exchange of an intraframework metal ion in a MOF that contains metal ions in discrete as well as polymeric SBUs is heretofore unprecedented.
由具有固有凹面特征、刚性核心和外围灵活性的三齿三酸H3L构建的中性锌金属有机框架（Zn-MOF）中的金属离子被发现存在于两种不同的次级结构单元（SBU）中，即0维和1维。这使得首次能够研究位点选择性的合成后金属交换（PSME），并对比配位聚合物中两种不同环境下金属离子的反应活性。离散环境中锌离子的位点选择性金属转移以单晶到单晶（SCSC）的方式发生，涉及铁（III）、钌（III）、铜（II）、钴（II）等金属离子，而作为1维SBU一部分的那些金属离子保持结构完整性，从而产生了传统方法无法获得的新型双金属MOF。据我们所知，在包含离散和聚合SBU中金属离子的MOF中，框架内金属离子的位点选择性合成后交换迄今为止是前所未有的。
