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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 rigger 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.



0305 Organic Chemistry, 0302 Inorganic Chemistry, 0306 Physical Chemistry (incl. Structural), 0303 Macromolecular and Materials Chemistry

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Chemical Society Reviews

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Royal Society of Chemistry
Royal Commission for the Exhibition of 1851 (RF478/2016)
Engineering and Physical Sciences Research Council (EP/K039520/1)
Engineering and Physical Sciences Research Council (EP/P027067/1)
European Research Council (695009)
D.A.R. acknowledges the Gates Cambridge Trust. B.S.P. acknowledges the Royal Commission for the Exhibition of 1851 Research Fellowship and the Fellowship from Corpus Christi College, Cambridge. This work was also supported by the UK Engineering and Physical Sciences Research Council (EPSRC, EP/P027067/1) and the European Research Council (695009).