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Issue 2, 2018
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Covalent post-assembly modification in metallosupramolecular chemistry

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A growing variety of covalent reactions have been employed to achieve the post-assembly modification (PAM) of self-assembled metallosupramolecular complexes. Covalent PAM enables the late-stage derivatisation of pre-assembled parent complexes in a modular fashion, thus expanding the chemical space available for supramolecular synthesis. The oldest and most widespread implementation of covalent PAM is in metal-preorganised covalent synthesis. Recent work, however, has broadened the scope of covalent PAM to include: protocols for efficiently grafting new functionalities onto supramolecular architectures, reactions that permanently ‘lock-down’ metastable complexes, and covalent bond-forming stimuli that trigger controlled structural transformations between distinct supramolecular species. This review highlights key examples of each of these distinct kinds of covalent PAM in metallosupramolecular chemistry, before providing a perspective upon future challenges and opportunities.

Graphical abstract: Covalent post-assembly modification in metallosupramolecular chemistry

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Article information

19 Sep 2017
First published
16 Nov 2017

Chem. Soc. Rev., 2018,47, 626-644
Article type
Review Article

Covalent post-assembly modification in metallosupramolecular chemistry

D. A. Roberts, B. S. Pilgrim and J. R. Nitschke, Chem. Soc. Rev., 2018, 47, 626
DOI: 10.1039/C6CS00907G

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