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

Abstract 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...

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Main Authors: Qiong-Yan Hong, Bin Huang, Meng-Xiang Wu, Jun-Yao Jiang, Hai-Bo Yang, Xiao-Li Zhao, Guido H. Clever, Xueliang Shi
Format: Article
Language:English
Published: Nature Portfolio 2025-03-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-57876-6
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author Qiong-Yan Hong
Bin Huang
Meng-Xiang Wu
Jun-Yao Jiang
Hai-Bo Yang
Xiao-Li Zhao
Guido H. Clever
Xueliang Shi
author_facet Qiong-Yan Hong
Bin Huang
Meng-Xiang Wu
Jun-Yao Jiang
Hai-Bo Yang
Xiao-Li Zhao
Guido H. Clever
Xueliang Shi
author_sort Qiong-Yan Hong
collection DOAJ
description Abstract 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.
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issn 2041-1723
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publishDate 2025-03-01
publisher Nature Portfolio
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series Nature Communications
spelling doaj-art-5aa5d4f04cde4e45aea2c46952cd03c92025-08-20T02:56:09ZengNature PortfolioNature Communications2041-17232025-03-0116111310.1038/s41467-025-57876-6Self-assembly, interlocking, interconversion and anion-binding catalysis in phenoxazine-based Pd2L4 and Pd4L8 coordination cagesQiong-Yan Hong0Bin Huang1Meng-Xiang Wu2Jun-Yao Jiang3Hai-Bo Yang4Xiao-Li Zhao5Guido H. Clever6Xueliang Shi7State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal UniversityState Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal UniversityState Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal UniversityState Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal UniversityState Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal UniversityState Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal UniversityDepartment of Chemistry and Chemical Biology, TU Dortmund UniversityState Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal UniversityAbstract 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.https://doi.org/10.1038/s41467-025-57876-6
spellingShingle Qiong-Yan Hong
Bin Huang
Meng-Xiang Wu
Jun-Yao Jiang
Hai-Bo Yang
Xiao-Li Zhao
Guido H. Clever
Xueliang Shi
Self-assembly, interlocking, interconversion and anion-binding catalysis in phenoxazine-based Pd2L4 and Pd4L8 coordination cages
Nature Communications
title Self-assembly, interlocking, interconversion and anion-binding catalysis in phenoxazine-based Pd2L4 and Pd4L8 coordination cages
title_full Self-assembly, interlocking, interconversion and anion-binding catalysis in phenoxazine-based Pd2L4 and Pd4L8 coordination cages
title_fullStr Self-assembly, interlocking, interconversion and anion-binding catalysis in phenoxazine-based Pd2L4 and Pd4L8 coordination cages
title_full_unstemmed Self-assembly, interlocking, interconversion and anion-binding catalysis in phenoxazine-based Pd2L4 and Pd4L8 coordination cages
title_short Self-assembly, interlocking, interconversion and anion-binding catalysis in phenoxazine-based Pd2L4 and Pd4L8 coordination cages
title_sort self assembly interlocking interconversion and anion binding catalysis in phenoxazine based pd2l4 and pd4l8 coordination cages
url https://doi.org/10.1038/s41467-025-57876-6
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