Halogen bonding versus hydrogen bonding in driving self-assembly and performance of light-responsive supramolecular polymers

Arri Priimagi (Corresponding Author), Gabriella Cavallo, Alessandra Forni, Mikael Gorynsztejn-Leben, Matti Kaivola, Pierangelo Metrangolo (Corresponding Author), Roberto Milani, Atsushi Shishido, Tullio Pilati, Giuseppe Resnati (Corresponding Author), Giancarlo Terraneo

    Research output: Contribution to journalArticleScientificpeer-review

    178 Citations (Scopus)


    Halogen bonding is arguably the least exploited among the many non‐covalent interactions used in dictating molecular self‐assembly. However, its directionality renders it unique compared to ubiquitous hydrogen bonding. Here, the role of this directionality in controlling the performance of light‐responsive supramolecular polymers is highlighted. In particular, it is shown that light‐induced surface patterning, a unique phenomenon occurring in azobenzene‐containing polymers, is more efficient in halogen‐bonded polymer–azobenzene complexes than in the analogous hydrogen‐bonded complexes. A systematic study is performed on a series of azo dyes containing different halogen or hydrogen bonding donor moieties, complexed to poly(4‐vinylpyridine) backbone. Through single‐atom substitution of the bond‐donor, control of both the strength and the nature of the noncovalent interaction between the azobenzene units and the polymer backbone is achieved. Importantly, such substitution does not significantly alter the electronic properties of the azobenzene units, hence providing us with unique tools in studying the structure–performance relationships in the light‐induced surface deformation process. The results represent the first demonstration of light‐responsive halogen‐bonded polymer systems and also highlight the remarkable potential of halogen bonding in fundamental studies of photoresponsive azobenzene‐containing polymers.
    Original languageEnglish
    Pages (from-to)2572-2579
    JournalAdvanced Functional Materials
    Issue number12
    Publication statusPublished - 2012
    MoE publication typeA1 Journal article-refereed


    • Halogen bonding
    • self-assembly
    • surface relief gratings
    • optically active materials
    • supramolecular polymers


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