Moderated Basicity of Endohedral Amine Groups in an Octa‐Cationic Self‐Assembled Cage

Wu, Hoi‐Ting; Camara, Bryce da; Williams, Colin J.; Mueller, Leonard J.; Julian, Ryan R.; Hooley, Richard J.

doi:10.1002/ange.202117011

Angewandte Chemie

2022

DOI: 10.1002/ange.202117011

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Moderated Basicity of Endohedral Amine Groups in an Octa‐Cationic Self‐Assembled Cage

Hoi‐Ting Wu

Bryce da Camara

Colin J. Williams

et al.

Abstract: A self‐assembled FeII4L6 cage was synthesized with 12 internal amines in the cavity. The cage forms as the dodeca‐ammonium salt, despite the cage carrying an overall 8+ charge at the metal centers, extracting protons from displaced water in the reaction. Despite this, the basicity of the internal amines is lower than their counterparts in free solution. The 12 amines have a sliding scale of basicity, with a ≈6 pKa unit difference between the first and last protons to be removed. This moderation of side‐chain b… Show more

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Cited by 9 publications

References 57 publications

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An Organo‐Palladium Host Built from a Dynamic Macrocyclic Ligand: Adaptive Self‐Assembly, Induced‐Fit Guest Binding, and Catalysis

Yan

Cai

et al. 2022

Angewandte Chemie

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Artificial hosts with rich conformational dynamics are attractive to supramolecular chemists due to their adaptive guest‐binding properties and enzyme‐like catalytic functions. We report here the adaptive self‐assembly and host‐guest catalysis of a new water‐soluble organo‐palladium host (Pd2L2) built from a pyridinium‐bonded macrocyclic ligand (L) and cis‐blocked palladium corners (Pd). While the direct self‐assembly of L with Pd gives rise to a dynamic mixture of products, both neutral polyaromatic hydrocarbons and an anionic polyoxometalate cluster (W10O324−) can template the dominant formation of the Pd2L2 host. Guest‐adaptive conformational changes and induced‐fit cavity deformation of the Pd2L2 host have been clearly observed in the crystal structures. Moreover, the installation of the electron‐rich W10O324− cluster within the cationic redox‐active host (W10O32⊂Pd2L2) facilitates the efficient and selective C−H photooxidation of toluene derivatives to aldehyde products under mild conditions, thus representing an ideal platform for green supramolecular catalysis.

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An Organo‐Palladium Host Built from a Dynamic Macrocyclic Ligand: Adaptive Self‐Assembly, Induced‐Fit Guest Binding, and Catalysis

Yan

Cai

et al. 2022

Angewandte Chemie

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Tetramine Aspect Ratio and Flexibility Determine Framework Symmetry for Zn₈L₆Self‐Assembled Structures

et al. 2023

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We derive design principles for the assembly of rectangular tetramines into Zn8L6 pseudo‐cubic coordination cages. Because of the rectangular, as opposed to square, geometry of the ligand panels, and the possibility of either Δ or Λ handedness of each metal center at the eight corners of the pseudo‐cube, many different cage diastereomers are possible. Each of the six tetra‐aniline subcomponents investigated in this work assembled with zinc(II) and 2‐formylpyridine in acetonitrile into a single Zn8L6 pseudo‐cube diastereomer, however. Each product corresponded to one of four diastereomeric configurations, with T, Th, S6 or D3 symmetry. The preferred diastereomer for a given tetra‐aniline subcomponent was shown to be dependent on its aspect ratio and conformational flexibility. Analysis of computationally modeled individual faces or whole pseudo‐cubes provided insight as to why the observed diastereomers were favored.

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Allosterically Regulated Guest Binding Determines Framework Symmetry for an Fe^II₄L₄ Cage

et al. 2023

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Self-assembly of a flexible tritopic aniline and 3-substituted 2-formylpyridine subcomponents around iron(II) templates gave rise to a low-spin Fe II 4 L 4 capsule, whereas a high-spin Fe II 3 L 2 sandwich species formed when a sterically hindered 6-methyl-2-formylpyridine was used. The Fe II 4 L 4 cage adopted a new structure type with S 4 symmetry, having two mer-Δ and two mer-Ʌ metal vertices, as confirmed by NMR and X-ray crystallographic analysis. The flexibility of the facecapping ligand endows the resulting Fe II 4 L 4 framework with conformational plasticity, enabling it to adapt structurally from S 4 to T or C 3 symmetry upon guest binding. The cage also displayed negative allosteric cooperativity in simultaneously binding different guests within its cavity and at the apertures between its faces.

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Moderated Basicity of Endohedral Amine Groups in an Octa‐Cationic Self‐Assembled Cage

Cited by 9 publications

References 57 publications

An Organo‐Palladium Host Built from a Dynamic Macrocyclic Ligand: Adaptive Self‐Assembly, Induced‐Fit Guest Binding, and Catalysis

An Organo‐Palladium Host Built from a Dynamic Macrocyclic Ligand: Adaptive Self‐Assembly, Induced‐Fit Guest Binding, and Catalysis

Tetramine Aspect Ratio and Flexibility Determine Framework Symmetry for Zn₈L₆Self‐Assembled Structures

Allosterically Regulated Guest Binding Determines Framework Symmetry for an Fe^II₄L₄ Cage

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Moderated Basicity of Endohedral Amine Groups in an Octa‐Cationic Self‐Assembled Cage

Cited by 9 publications

References 57 publications

An Organo‐Palladium Host Built from a Dynamic Macrocyclic Ligand: Adaptive Self‐Assembly, Induced‐Fit Guest Binding, and Catalysis

An Organo‐Palladium Host Built from a Dynamic Macrocyclic Ligand: Adaptive Self‐Assembly, Induced‐Fit Guest Binding, and Catalysis

Tetramine Aspect Ratio and Flexibility Determine Framework Symmetry for Zn8L6Self‐Assembled Structures

Allosterically Regulated Guest Binding Determines Framework Symmetry for an FeII4L4 Cage

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Product

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Tetramine Aspect Ratio and Flexibility Determine Framework Symmetry for Zn₈L₆Self‐Assembled Structures

Allosterically Regulated Guest Binding Determines Framework Symmetry for an Fe^II₄L₄ Cage