Iminodibenzyl[n]arenes: prismatic structure, selective binding, and room-temperature phosphorescence prolonged by molecular rivet

IF 9.7 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Science China Chemistry Pub Date : 2025-06-03 DOI:10.1007/s11426-025-2659-3

Nan Pan, Ziyan Wu, Hao Hu, Linbin Yao, Jialin Xie, Kelong Zhu, Chunman Jia

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Abstract

Macrocyclic hosts capable of specific molecular recognition are crucial for advancing supramolecular chemistry, but rarely display phosphorescent activity. Herein, we report a new class of macrocycles, iminodibenzyl[n]arenes (IB[n]As, n = 3, 4), that exhibit unusual green room-temperature phosphorescence (RTP). The uniqueness of IB[4]A is a concave double-cavity structure with an RTP lifetime of 3.82 ms. Although IB[3]A has a shorter RTP lifetime of 1.91 ms, it features outstanding size-selective binding for guest molecules due to its tendency for prismatic cavity formation. This was supported by single-crystal analysis, density functional theory calculations, and host-guest binding experiments involving eight different-sized cationic guests. The structural complementarity between IB[3]A and 1,4-diazabicyclo[2.2.2]octane cation G4 is particularly notable, affording a stronger affinity (K = 2524 M⁻¹) compared to others. Accordingly, encapsulating this suitable “guest rivet” induces a more rigid microenvironment, prolonging the RTP lifetime to 8.99 ms. This study bridges selective molecular recognition and RTP modulation in macrocyclic hosts, facilitating the architectural design of complex molecules and offering diverse post-synthetic tunability for phosphorescent compounds.

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亚氨基二苄基芳烃：柱状结构、选择性结合及分子铆钉延长室温磷光

具有特异性分子识别能力的大环寄主对推进超分子化学至关重要，但很少显示磷光活性。在此，我们报道了一类新的大环，亚氨基二苄基[n]芳烃（IB[n]As, n = 3,4），表现出不寻常的室温绿色磷光（RTP）。IB[4]a的独特之处在于其凹双腔结构，RTP寿命为3.82 ms。虽然IB[3]A的RTP寿命较短，为1.91 ms，但由于其倾向于形成棱柱形空腔，因此对客体分子具有突出的尺寸选择性结合。这得到了单晶分析、密度泛函理论计算和涉及8种不同大小阳离子客体的主客体结合实验的支持。IB[3]A与1,4-重氮杂环[2.2.2]辛烷阳离子G4之间的结构互补性尤为显著，与其他阳离子相比具有更强的亲和力（K = 2524 M−1）。因此，封装这个合适的“来宾铆钉”会产生一个更严格的微环境，将RTP生命周期延长到8.99毫秒。该研究在选择性分子识别和大环宿主的RTP调节之间架起了桥梁，为复杂分子的结构设计提供了便利，并为磷光化合物提供了多种合成后的可调节性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Science China Chemistry CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

7.30%

发文量

3787

审稿时长

2.2 months

期刊介绍： Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field. Categories of articles include: Highlights. Brief summaries and scholarly comments on recent research achievements in any field of chemistry. Perspectives. Concise reports on thelatest chemistry trends of interest to scientists worldwide, including discussions of research breakthroughs and interpretations of important science and funding policies. Reviews. In-depth summaries of representative results and achievements of the past 5–10 years in selected topics based on or closely related to the research expertise of the authors, providing a thorough assessment of the significance, current status, and future research directions of the field.