Adaptive coordination-driven supramolecular chemistry based on conformationally flexible pre-organized luminescent Cu(I) precursors paves the way to the ready formation of an intricate supramolecular scaffold possessing intrinsic luminescence properties. A formal ring extension of a tetrametallic Cu(I) metallacycle bearing Thermally Activated Delayed Fluorescence (TADF) properties can thus be carried out, affording a new hexametallic Cu(I) metallacycle 1 bearing modulated solid-state TADF properties. Attempts to adapt this ring extension process to the formation of targeted heterometallic Au₂Cu₄ and Pt₂Cu₈ assemblies led to the unexpected and ready formation of the Au₂Cu₁₀ and Pt₄Cu₁₁ derivatives 2 and 3, respectively. These outcomes strengthen the scope and perspectives of adaptive coordination-driven supramolecular chemistry compared to those of conventional coordination-driven supramolecular chemistry. Indeed, it guides concerted intramolecular fragmentation and redistribution of the particular building blocks used, affording selectively supramolecular scaffolds of higher nuclearity and complexity. The study of the solid-state photophysical properties of the assemblies 2 and 3 highlights enhanced and original behaviors, in which the heavy metal spin–orbit coupling values significantly influence the relaxation processes centered on the Cu(I) metal centers.

中文翻译：

---

分子内重排由适应性协调驱动的反应导向高发光多核Cu（I）组装

基于构象柔性预组织的发光Cu（I）前体的自适应配位驱动超分子化学为易于形成具有固有发光特性的复杂超分子支架铺平了道路。因此，可以进行具有热活化延迟荧光（TADF）性质的四金属Cu（I）金属环的正式的环延伸，从而提供具有调制的固态TADF性质的新的六金属Cu（I）金属环1。尝试使这种扩环过程适应于形成目标异金属Au ₂ Cu ₄和Pt ₂ Cu ₈组装导致意外和现成的Au ₂ Cu ₁₀和Pt ₄ Cu ₁₁衍生物2和3的形成。与传统的配位驱动的超分子化学相比，这些结果加强了自适应配位驱动的超分子化学的范围和前景。的确，它指导了所使用的特定构件的分子内一致的碎裂和重新分布，从而提供了具有更高核性和复杂性的选择性超分子支架。组件2和3的固态光物理性质的研究突出显示了增强的和原始的行为，其中重金属自旋-轨道耦合值显着影响以Cu（I）金属中心为中心的弛豫过程。