Abstract

Previously, we introduced a series of anion-binding interpenetrated double-cages based on phenothiazine and its mono- and di-S-oxygenated derivatives. Here, we complete the structural comparison of the three related assemblies by an X-ray single crystal analysis of the sulfone derivative. We further show that the three palladium cages coexist in solution upon post-assembly mixing due to the very slow ligand exchange whereas treatment of binary mixtures of the corresponding ligands with Pd(II) leads to the formation of mixed cages comprising a statistical ligand distribution. In contrast, mixtures of one of these ligands with a shorter ligand derivative lead to narcissistic self-assembly into a double-cage and a coexisting small monomeric cage, regardless of the order of mixing and Pd(II) addition.

Highlights

  • Self-assembled coordination cages[1] have found application in various areas such as selective guest binding,[2] stabilisation of reactive compounds,[3] catalysis,[4] redoxactive[5] and light switchable materials.[6]

  • The successful X-ray structure determination of [Pd4L38] allows for a systematic comparison between all three members of the family of interpenetrated cages based on phenothiazine

  • The effect of the extra oxygen substituent attached to each of the eight sulfur atoms in [Pd4L38] has essentially two structural implications: first, it leads to a displacement of the sulfur atoms of the interpenetrating ligands away from the inner Pd atom of the other cage substructure, and second, it influences the bending angle of the ligands with respect to the non-flat phenothiazine component

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Summary

Introduction

Self-assembled coordination cages[1] have found application in various areas such as selective guest binding,[2] stabilisation of reactive compounds,[3] catalysis,[4] redoxactive[5] and light switchable materials.[6]. All three long ligands were previously shown to quantitatively yield interpenetrated double-cages [Pd4L1–38] upon treatment with the metal source [Pd-(CH3CN)4](BF4)[2] in acetonitrile solution.[10] The structures were found to contain BF4− counter anions encapsulated in their two outer pockets and one inside their central cavity.

Results
Conclusion

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