Highly two‐photon and X‐ray excited long‐persistent luminescence in a crystalline host‐guest aggregate

Abstract

AbstractAs a unique type of supramolecular self‐assemblies, crystalline host‐guest aggregates have attracted extensive interests in multiple application fields. Herein, a crystalline host‐guest aggregate LIFM‐HG1 was obtained with curcubit[8]uril as the host and carboxypyridinium salt as the guest. Single‐crystal structural analysis indicates that the presence of abundant weak interactions in LIFM‐HG1 provides a rigid environment for the guest molecule and effectively blocks the external quenchers. Spectral analysis and theoretical calculations confirm the presence of robust triplet energy levels in LIFM‐HG1. Even more impressively, the intersystem crossing channels of the guest molecules are greatly opened up after the formation of the crystalline host‐guest aggregate, resulting in a large kisc of 6.70 × 107 s−1 at room temperature for LIFM‐HG1 (which is ∼0 for pure guest), leading to fascinating multichannel (including one‐photon, two‐photon, and X‐ray) excited LPL properties. In addition, the crystalline LIFM‐HG1 has a much higher triplet state luminescence efficiency under X‐ray and two‐photon excitation than that under single‐photon excitation (AP/AF = 86.8, 44.8, 10.7 under the three circumstances, respectively). And the phosphorescent emission intensity of LIFM‐HG1 is 27.6 times higher than that of the crystalline guest under X‐ray excitation. As a result, LIFM‐HG1 shows a long afterglow retention time under both single‐ and two‐photon excitation, and an impressive afterglow retention time of 1 s under X‐ray excitation. Furthermore, the excellent lysosomal targeting and low cytotoxicity by the formation of host‐guest aggregate makes LIFM‐HG1 promising to be used as a novel lysosomal‐targeted two‐photon excited phosphorescent tracer.