Unprecedented Pd(II) Metal–Organic Cages for Simultaneous Adsorption of Iodine Species

IF 7.1 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2026-10-13 DOI:10.1021/acs.chemmater.6c01650

Risikeshan Pradhan,Raghunath Singha,Pijush De,Monotosh Dalapati,Pankaj Maity,Debashree Manna,Dipak Samanta

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引用次数: 0

Abstract

Abstract Metal–organic cages (MOCs) with unconventional topologies remain rare owing to the challenges associated with controlling coordination-driven self-assembly. Herein, we report the self-assembly of two unique Pd(II)-based coordination cages–peanut-shaped cage (C1, M18L14) and hemicage (C2, M12M2L22), from semiflexible tetratopic pyridyl ligands incorporating 9,10-dihydroanthracene and benzene backbones, respectively. Single-crystal X-ray diffraction studies reveal that cage C1 adopts a rare peanut-shaped structure comprising two interconnected cavities and both inward- and outward-oriented Pd(II) nodes, generating a highly electron-rich confined environment. In contrast, C2 forms an unprecedented boat-shaped architecture assembled through the cooperative incorporation of 90° and 180° Pd(II) acceptors within a single discrete cage. Despite their amorphous and nonporous nature, these assemblies demonstrate exceptional dual-capture performance toward volatile iodine species. Notably, C1 achieves iodine uptake capacities of 2.62 g g–1 under static vapor-phase conditions and 1.21 g g–1 under dynamic flow conditions, together with efficient CH3I adsorption of up to 1.05 g g–1 at 75 °C. Spectroscopic investigations and theoretical calculations reveal that the adsorption process is driven by synergistic charge-transfer interactions, polyiodide formation, electrostatic stabilization, and cavity confinement. Furthermore, both cages display excellent retention capability and recyclability, highlighting their potential as robust materials for radioactive iodine sequestration and environmental remediation.

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前所未有的pd （II）金属-有机笼同时吸附碘

具有非常规拓扑结构的金属有机笼（moc）由于控制坐标驱动的自组装相关的挑战而仍然很少见。本文报道了两种独特的Pd（II）基配位笼-花生形笼（C1, M18L14）和半笼（C2, M12M2L22），分别由含有9,10-二氢蒽和苯骨架的半柔性四异位吡啶配体自组装而成。单晶x射线衍射研究表明，C1笼采用了罕见的花生状结构，由两个相互连接的空腔和向内和向外的Pd（II）节点组成，形成了一个高度富电子的密闭环境。相比之下，C2形成了一个前所未有的船形结构，通过将90°和180°Pd（II）受体合作结合在一个单独的笼中。尽管它们具有无定形和无孔性质，但这些组件对挥发性碘物种表现出特殊的双捕获性能。值得注意的是，C1在静态气相条件下的碘吸收率为2.62 g - 1，在动态流动条件下的吸收率为1.21 g - 1，在75℃下的CH3I吸收率高达1.05 g - 1。光谱研究和理论计算表明，吸附过程是由协同电荷转移相互作用、多碘化物形成、静电稳定和腔约束驱动的。此外，这两种笼都显示出优异的保留能力和可回收性，突出了它们作为放射性碘隔离和环境修复的坚固材料的潜力。

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

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.