Highly two‐photon and X‐ray excited long‐persistent luminescence in a crystalline host‐guest aggregate
Qiang‐Sheng Zhang, Xiaodong Zhang, Jia‐Yi Zhuang, Mei Pan
Abstract
Abstract As 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 k isc of 6.70 × 10 7 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 ( A P /A F = 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.