Giant Electroactive M4L6 Tetrahedral Host Self-Assembled with Fe(II) Vertices and Perylene Bisimide Dye Edges

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• 作者：Kingsuk Mahata ; Peter D. Frischmann ; Frank W眉rthner
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：October 16, 2013
• 年：2013
• 卷：135
• 期：41
• 页码：15656-15661
• 全文大小：381K
• 年卷期：v.135,no.41(October 16, 2013)
• ISSN：1520-5126

文摘

Self-assembly of octahedral Fe(II) ions and linear perylene bisimide (PBI) dyes with 2,2鈥?bipyridine groups covalently attached at the imide positions quantitatively yields an Fe₄(PBI)₆ tetrahedron by the directional bonding approach. With an edge length of 3.9 nm and estimated internal volume >950 脜³, tetrahedron T is one of the largest M₄L₆ tetrahedra ever reported. Importantly, many of the desirable photo- and electroactive properties of the PBI ligands are transferred to the nanoscale metallosupramolecule. Tetrahedron T absorbs strongly across the visible spectrum out to 650 nm and exhibits a total of 7 highly reversible electrochemical oxidation and reduction waves spanning a 3.0 V range. This facile cycling of 34 electrons between +18 and 鈭?6 charged species is likely enabled due to the porous nature of the tetrahedron that allows the necessary counterions to freely flow in and out of the host. Host鈥揼uest encapsulation of C₆₀ by T in acetonitrile was studied by ¹³C NMR spectroscopy, UV鈥搗is spectroscopy, and ESI-MS, confirming that the tetrahedron is a suitable host for large, functional guest molecules.