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<p>Interpenetration is a phenomenon frequently encountered in self-assembled Pd<sub>2</sub>L<sub>4</sub>-type coordination cages, while the mechanism of the interpenetration process remains unclear. Here we show the synthesis and solvent-mediated interconversion of highly soluble phenoxazine-based monomeric cage <b>1</b> and corresponding interlocked dimer <b>2</b>. We succeed in the isolation and single-crystal structure analysis of both <b>1</b> and <b>2</b> with the same guest anion by changing the solvents utilized in self-assembly. The monomeric-to-dimeric cage conversion occurs by heating in weakly coordinating solvents, while dimeric-to-monomeric cage conversion takes place through a disassembly and reassembly process in strongly coordinating solvents at low concentration or by the addition/removal of competing ligand. The interconversion may be driven by the distinct thermodynamic stabilities of <b>1</b> and <b>2</b> in different solvents. Additionally, Cl<sup>–</sup> anions template the interpenetration of <b>1</b> because of the strong chloride binding affinity of <b>2</b> which could serve as an anion-binding catalyst for the C–Cl bond cleavage.</p>

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Self-assembly, interlocking, interconversion and anion-binding catalysis in phenoxazine-based Pd2L4 and Pd4L8 coordination cages

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年3月13日

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  • Qiong-Yan Hong,
  • Bin Huang,
  • Meng-Xiang Wu,
  • Jun-Yao Jiang,
  • Hai-Bo Yang,
  • Xiao-Li Zhao,
  • Guido H. Clever,
  • Xueliang Shi

摘要

Interpenetration is a phenomenon frequently encountered in self-assembled Pd2L4-type coordination cages, while the mechanism of the interpenetration process remains unclear. Here we show the synthesis and solvent-mediated interconversion of highly soluble phenoxazine-based monomeric cage 1 and corresponding interlocked dimer 2. We succeed in the isolation and single-crystal structure analysis of both 1 and 2 with the same guest anion by changing the solvents utilized in self-assembly. The monomeric-to-dimeric cage conversion occurs by heating in weakly coordinating solvents, while dimeric-to-monomeric cage conversion takes place through a disassembly and reassembly process in strongly coordinating solvents at low concentration or by the addition/removal of competing ligand. The interconversion may be driven by the distinct thermodynamic stabilities of 1 and 2 in different solvents. Additionally, Cl– anions template the interpenetration of 1 because of the strong chloride binding affinity of 2 which could serve as an anion-binding catalyst for the C–Cl bond cleavage.