Stimuli-Responsive Polydiacetylene Based on the Self-Assembly of a Mercury-Bridged Macrocyclic Diacetylene Dimer

초록

The metal-mediated self-assembly process allows the well-directed and controlled construction of supramolecular architectures, and the assembled metal-ligand complexes display diverse functionalities depending on the composition of the complex template. Through the deliberate introduction of a metal-binding nucleobase, cytosine, to the macrocyclic diacetylene (MCDA), a macrocyclic ligand, CytMCDA, was synthesized. On account of the metal affinity of cytosine and the π-πinteraction of the diacetylene template, a Hg-coordinated unidirectional columnar self-assembly of CytMCDA was generated that formed into organic nanotubes. The monomeric CytMCDA-Hg is covalently cross-linked to the blue-phase macrocyclic polydiacetylene nanotubes (CytMCPDA-Hg) via UV-induced topochemical polymerization. CytMCPDA-Hg displayed a naked-eye-detectable sensing response toward heat and solvents with a brilliant blue-red chromatic transition. Moreover, owing to the high affinity of the mercury complex toward sulfur, CytMCPDA-Hg displayed a high sensitivity against thiols.

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