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Issue 16, 2014
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Metallophilicity-assisted assembly of phosphine-based cage molecules

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Abstract

A family of supramolecular cage molecules has been obtained via self-assembly of the phosphine–gold coordination complexes following an aurophilicity-driven aggregation approach. Use of the di- (PP) or tridentate (PPP) phosphine ligands Pn (n = 2, 3) with rigid polyaromatic backbones leads to clean formation of the coordination Pn(Au(tht))nn+ species, sequential treatment of which with H2O/NEt3 and excess of H2NBut gives the finite 3D structures of two major types. The cylindrical-like hexametallic cages [(PPAu2)33-NBut)2]2+ are based on the diphosphines PP = 1,4-bis(diphenylphosphino)benzene (1), 4,4′-bis(diphenylphosphino)biphenyl (2), 4,4′′-bis(diphenylphosphino)terphenyl (3), while the triphosphine PPP (1,3,5-tris(diphenylphosphinophenyl)benzene) produces a tetrahedral dodecagold complex [(PPPAu3)43-NBut)4]4+ (4). The cages 1–4 have been studied using the ESI-MS and 1H, 31P NMR spectroscopy, and the crystal structures of 1 and 4 were determined by an X-ray diffraction study. The NMR spectroscopic investigations showed that cylindrical complexes 1–3 undergo twisting-like interconversion of the helical PM isomers in solution, while 4 is a stereochemically rigid compound retaining its axially chiral architecture. The difference in dynamic behavior was rationalized using computational studies with density functional methods.

Graphical abstract: Metallophilicity-assisted assembly of phosphine-based cage molecules

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Publication details

The article was received on 28 Dec 2013, accepted on 04 Feb 2014 and first published on 05 Mar 2014


Article type: Paper
DOI: 10.1039/C3DT53645A
Citation: Dalton Trans., 2014,43, 6236-6243
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    Metallophilicity-assisted assembly of phosphine-based cage molecules

    J. R. Shakirova, E. V. Grachova, A. J. Karttunen, V. V. Gurzhiy, S. P. Tunik and I. O. Koshevoy, Dalton Trans., 2014, 43, 6236
    DOI: 10.1039/C3DT53645A

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