A Woven Supramolecular Metal‐Organic Framework Comprising a Ruthenium Bis(terpyridine) Complex and Cucurbit[8]uril: Enhanced Catalytic Activity toward Alcohol Oxidation

• Published in: ChemPlusChem (Weinheim, Germany) Vol. 85; no. 7; pp. 1498 - 1503
• Main Authors: Zhang, Yun‐Chang, Xu, Zi‐Yue, Wang, Ze‐Kun, Wang, Hui, Zhang, Dan‐Wei, Liu, Yi, Li, Zhan‐Ting
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 01.07.2020; Wiley Blackwell (John Wiley & Sons)
• Subjects: alcohol oxidation; Chemistry; Chemistry, Multidisciplinary; heterogeneous catalysis; metal-organic frameworks; Physical Sciences; ruthenium; Science & Technology; self-assembly; heterogeneous catalysis; PHOTOSENSITIZERS; DRIVEN; PORES; metal-organic frameworks; alcohol oxidation; ruthenium; self-assembly; ASSEMBLIES; DNA; LUMINESCENT; ENRICHMENT; EMISSION
• ISSN: 2192-6506; 2192-6506
• DOI: 10.1002/cplu.202000391

The self‐assembly of a diamondoid woven supramolecular metal–organic framework wSMOF‐1 has been achieved from intertwined [Ru(tpy)2]2+ (tpy=2,2′,6′,2′′‐terpyridine) complex M1 and cucurbit[8]uril (CB[8]) in water, where the intermolecular dimers formed by the appended aromatic arms of M1 are encapsulated in CB[8]. wSMOF‐1 exhibits ordered pore periodicity in both water and the solid state, as confirmed by a combination of 1H NMR spectroscopy, UV‐vis absorption, isothermal titration calorimetry, dynamic light scattering, small angle X‐ray scattering and selected area electron diffraction experiments. The woven framework has a pore aperture of 2.1 nm, which allows for the free access of both secondary and primary alcohols and tert‐butyl hydroperoxide (TBHP). Compared with the control molecule [Ru(tpy)2]Cl2, the [Ru(tpy)2]2+ unit of wSMOF‐1 exhibits a remarkably higher heterogeneous catalysis activity for the oxidation of alcohols by TBHP in n‐hexane. For the oxidation of 1‐phenylethan‐1‐ol, the yield of acetophenone was increased from 10 % to 95 %. A woven supramolecular metal‐organic framework is assembled from an intertwined [Ru(tpy)2]2+ complex and cucurbit[8]uril. Regularly weaving the [Ru(tpy)2]2+ units into the framework leads to a significant cage effect, which enables the intrinsically low‐activity complexes to exhibit remarkably high catalytic activity for the oxidation of primary and secondary alcohols. For the oxidation of secondary alcohols, the yields of the corresponding ketones can be increased from ≤10 %, obtained with the [Ru(tpy)2]2+ control, to ≥92 %.