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We developed a host-guest ATP responsive strategy for efficient intracellular delivery of phosphopeptides, employing a pegylated arginine clustered calix[5]arene nanocarrier system that has great capability of recognizing the phosphate moieties on peptides and penetrating the cell membrane.A co-crystal was obtained based on donor-acceptor interactions. The obvious charge transfer from the linear donor to the triangular acceptor units results in a quasi-two-dimensional CT complex with excellent near-infrared photothermal conversion effic