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Selective Anion Binding Drives the Formation of AgI8L6and AgI12L6Six-Stranded Helicates

Research output: Contribution to journalArticlepeer-review

Charlie T. McTernan, Tanya K. Ronson, Jonathan R. Nitschke

Original languageEnglish
Pages (from-to)664-670
Number of pages7
JournalJournal of the American Chemical Society
Volume143
Issue number2
DOIs
Published20 Jan 2021

Bibliographical note

Funding Information: This work was supported by the Engineering and Physical Sciences Research Council (EPSRC, EP/P027067/1) and the European Research Council (695009). We thank the University of Cambridge Mass Spectrometry Service Centre for high-resolution mass spectrometry and Diamond Light Source (UK) for synchrotron beamtime on I19 (CY21497). C.T.M. thanks the Leverhulme Trust and the Isaac Newton Trust, and Sidney Sussex College, Cambridge, for Fellowship support. Publisher Copyright: © 2020 American Chemical Society. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

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Abstract

Here we describe the formation of an unexpected and unique family of hollow six-stranded helicates. The formation of these structures depends on the coordinative flexibility of silver and the 2-formyl-1,8-napthyridine subcomponent. Crystal structures show that these assemblies are held together by Ag4I, Ag4Br, or Ag6(SO4)2 clusters, where the templating anion plays an integral structure-defining role. Prior to the addition of the anionic template, no six-stranded helicate was observed to form, with the system instead consisting of a dynamic mixture of triple helicate and tetrahedron. Six-stranded helicate formation was highly sensitive to the structure of the ligand, with minor modifications inhibiting its formation. This work provides an unusual example of mutual stabilization between metal clusters and a self-assembled metal-organic cage. The selective preparation of this anisotropic host demonstrates new modes of guiding selective self-assembly using silver(I), whose many stable coordination geometries render design difficult.

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