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Based on saddle-shaped cyclooctathiophene (COTh) as a building block, ligands 2 and 3 were synthesized bearing 3- or 4-substituted pyridyl groups as coordination groups, which showed strong gelation abilities with AgBF4 in several solvents at room temperature. This Ag+-induced metallogel exhibited outstanding stimuli-responsive properties upon addition of halogen ions, acetonitrile or H2O.Self-adhesiveness is highly desirable for conformal and seamless wearable electronics. Here, a starch-tackifying method is proposed to obtain adhesive a