Development of crystalline porous materials with luminescent properties have gradually attracted attention for their potential applications in drug delivery, bioimaging, photoelectronic and so on. To date, it is a formidable challenge to rationally design porous phosphorescent materials. Herein, we have reported a chemical strategy of breaking π-conjugated structures of phosphorescent molecules by alkyl chain to achieve supramolecular organic framework (SOFs) with visible ultralong phosphorescence (lifetime > 600 ms). The molecules having broken π-conjugation by flexible alkyl chain will be beneficial to produce short-range π-π stacking for forming luminescent SOFs. Effective π-π stacking between chromophores stabilized triplet excitons to contribute to ultra-long phosphorescence. This work demonstrates a new approach to design porus materials with ultralong phosphorescence and will expand the potential applications of organic phosphorescent crystals with diverse pores.

具有发光特性的结晶性多孔材料的开发在药物递送，生物成像，光电等领域的潜在应用已逐渐引起人们的关注。迄今为止，合理设计多孔磷光材料是一个巨大的挑战。在本文中，我们已经报道了一种化学策略，该化学策略通过烷基链破坏磷光分子的π共轭结构，以实现超分子有机骨架（SOF），并具有可见的超长磷光（寿命> 600 ms）。具有通过柔性烷基链断裂的π-共轭的分子将有利于产生用于形成发光SOF的短程π-π堆叠。发色团之间有效的π-π堆叠稳定了三重态激子，从而促进了超长磷光。