Metallacarborane-Based Metal鈥揙rganic Framework with a Complex Topology

详细信息    查看全文

• 作者：Robert D. Kennedy ; Daniel J. Clingerman ; William Morris ; Christopher E. Wilmer ; Amy A. Sarjeant ; Charlotte L. Stern ; Michael O鈥橩eeffe ; Randall Q. Snurr ; Joseph T. Hupp ; Omar K. Farha ; Chad A. Mirkin
• 刊名：Crystal Growth & Design
• 出版年：2014
• 出版时间：March 5, 2014
• 年：2014
• 卷：14
• 期：3
• 页码：1324-1330
• 全文大小：471K
• 年卷期：v.14,no.3(March 5, 2014)
• ISSN：1528-7505

文摘

The long, linear cobalt(III) bis(dicarbollide)-based bis(isophthalic acid) anion was synthesized as a tetraphenylphosphonium salt in five steps from 8-iodo-closo-1,2-C₂B₁₀H₁₁. The solvothermal reaction between the anionic bis(isophthalic acid) linker and copper(II) nitrate in acidified DMF yielded single crystals. Despite the tendency for copper(II) and analogous linear tetraacids to form members of an isoreticular family of metal鈥搊rganic frameworks (MOFs) with the fof topology, single-crystal X-ray diffraction analysis revealed the growth of three different frameworks. These MOFs, NU-150, NU-151, and NU-152, have three distinct topologies: fof, sty, and hbk, respectively. NU-152 has a novel quadrinodal topology in which cuboctahedral coordination polyhedra are each connected to 10 neighboring polyhedra via the cobalt bis(dicarbollide) portions of the linkers. The formation of these frameworks illustrates the limitations of structure prediction in MOF chemistry and the possibility of using flexible linkers to generate unexpected topologies. Furthermore, this work represents the first example of the incorporation of an anionic bis(dicarbollide) unit into a MOF.