Noncovalent Polymerization-Activated Ultrastrong Near-Infrared Room-Temperature Phosphorescence Energy Transfer Assembly in Aqueous Solution.

Abstract

Noncovalent macrocycle-confined supramolecular purely organic room-temperature phosphorescence (RTP) is a current research hotspot. Herein, a high-efficiency noncovalent polymerization-activated near-infrared (NIR)-emissive RTP-harvesting system in aqueous solution based on the stepwise confinement of cucurbit[7]uril (CB[7]) and β-cyclodextrin-grafted hyaluronic acid (HACD), is reported. Compared with the dodecyl-chain-bridged 6-bromoisoquinoline derivative (G), the dumbbell-shaped assembly G⊂CB[7] presents an appeared complexation-induced RTP signal at 540nm via the first confinement of CB[7]. Subsequently, benefitting from the stepwise confinement encapsulation of the β-cyclodextrin cavity, the subsequent noncovalent polymerization of the binary G⊂CB[7] assembly enabled by HACD can contribute to the further-enhanced RTP emission intensity approximately eighttimes in addition to an increased lifetime from 59.0µs to 0.581ms. Moreover, upon doping a small amount of two types of organic dyes, Nile blue or tetrakis(4-sulfophenyl)porphyrin as an acceptor into the supramolecular confinement assembly G⊂CB[7] @ HACD, efficient RTP energy transfer occurs accompanied by a long-lived NIR-emitting performance (680 and 710nm) with a high donor/acceptor ratio. Intriguingly, the prepared RTP-harvesting system is successfully applied for targeted NIR imaging of living tumor cells by utilizing the targeting ability of hyaluronic acid, which provides a new strategy to create advanced water-soluble NIR phosphorescent materials.