Supramolecular copolymers constitute a fundamental new class of functional materials attracting burgeoning interest, but examples that display phosphorescence and long-lived excited states are rare. Herein, we describe the synthesis of sequential phosphorescent multi-block supramolecular copolymers in one and multiple dimensions using pincer Pt^II and Pd^II complexes as building blocks by manipulating out-of-equilibrium self-assemblies via the living supramolecular polymerization approach. Doping a small amount of Pt^II complexes (2 mol %) into the Pd^II assemblies significantly boosted the emission efficiency and radiative decay rate constant (Φ_em = 3.7%, k_r = 1.8 × 10⁴ s⁻¹ in Pd^II assemblies; Φ_em = 76.2%, k_r = 58.6 × 10⁴ s⁻¹ in Pt^II-Pd^II co-assemblies), which is ascribed to an external heavy-atom spin-orbital coupling effect arising from the doped Pt^II complex with a delocalized ³[dσ∗→π∗] excited state. The findings on Pt^II and Pd^II supramolecular copolymers with controlled sequences and greatly enhanced phosphorescence efficiencies open the door to new photofunctional and responsive luminescent metal-organic supramolecular materials.

超分子共聚物构成一类基本的新型功能材料，引起了人们的广泛关注，但很少有显示磷光和长寿命激发态的例子。在这里，我们描述了通过使用活泼的超分子聚合方法来操纵不平衡的自组装体，使用夹钳式Pt ^II和Pd ^II配合物作为结构单元，在一维和多维中顺序合成磷光多嵌段超分子共聚物。掺杂的Pt少量^II复合物（2摩尔％）到钯^II组件显著升压后的发射效率和辐射衰变速率常数（Φ _EM  = 3.7％，ķ _{- [R}  = 1.8×10Pd ^II组件为⁴ s ^-1；Φ _EM  = 76.2％，ķ _{- [R}  = 58.6×10 ⁴小号^-1中的Pt ^II -Pd ^II共同组件），这归因于从所产生的一个外部重原子自旋-轨道耦合效应掺杂的Pt ^II复合物与离域³ [dσ∗→π∗]激发态。具有可控序列和大大增强的磷光效率的Pt ^II和Pd ^II超分子共聚物的发现为新型的具有光功能和响应性的发光金属有机超分子材料打开了大门。