Maximized axial helicity in a Pd<sub>2</sub>L<sub>4</sub>cage: inverse guest size-dependent compression and mesocate isomerism

Bloch, Witold M.; Horiuchi, Shigeo; Holstein, Julian J.; Drechsler, Christoph; Wuttke, Axel; Hiller, Wolf; Mata, Ricardo A.; Clever, Guido H.

doi:10.1039/d2sc06629g

Cited by 14 publications

(6 citation statements)

References 86 publications

(120 reference statements)

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“…5(a), where helicity occurs without torsion restrictions, which is akin to recent work in Pd 2 L 4 cages. 58 Further, we see that there would be a mixed effect of turning off torsion restrictions on pore size; many unrestricted cages are collapsed, but the same seems to be true for unstable restricted cages with torsion restrictions. Shape persistence or porosity is not directly related to flexibility, although the average pore size 52 should be considered for flexible cages, rather than a static image, which provides a less clear image of cage porosity.…”

Section: Resultsmentioning

confidence: 81%

Systematic exploration of accessible topologies of cage molecules via minimalistic models

Tarzia,

Wolpert,

Jelfs

et al. 2023

Chem. Sci.

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Section: Resultsmentioning

confidence: 81%

Systematic exploration of accessible topologies of cage molecules via minimalistic models

Tarzia,

Wolpert,

Jelfs

et al. 2023

Chem. Sci.

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“…Finally, single crystals suitable for X-ray diffraction were obtained for species [Pd 2 AZU1 4 ] by slow diffusion of ethyl acetate in its DMSO solution (Figure ) and for [Pd 2 AZU2 4 ] by slow diffusion of diisopropyl ether in its acetonitrile solution (Figure a). [Pd 2 AZU1 4 ] adopts a lantern shape similar to previously reported structures, while [Pd 2 AZU2 4 ], due to its 8-isoquinoline donor groups, adopts a helical shape . Interestingly, in the latter structure both helical isomers cocrystallize as closely packed pairs, where the aromatic regions of both enantiomers stack together and therefore yield a distorted geometry (Figure S55).…”

Section: Resultsmentioning

confidence: 99%

“…[Pd 2 AZU1 4 ] adopts a lantern shape similar to previously reported structures, 5 while [Pd 2 AZU2 4 ], due to its 8isoquinoline donor groups, adopts a helical shape. 39 Interestingly, in the latter structure both helical isomers cocrystallize as closely packed pairs, where the aromatic regions of both enantiomers stack together and therefore yield a distorted geometry (Figure S55).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Guest-Induced Reversible Transformation between an Azulene-Based Pd₂L₄ Lantern-Shaped Cage and a Pd₄L₈ Tetrahedron

Walther,

Regeni,

Holstein

et al. 2023

J. Am. Chem. Soc.

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Azulene, a blue structural isomer of naphthalene, is introduced as the backbone for a new family of Pd(II)-based self-assemblies. Three organic ligands, equipped with varying donor groups, produce three [Pd2L4] cages of different cavity dimensions. Unexpectedly, the addition of organic disulfonate guests to the smallest lantern-shaped cage (featuring pyridine donors) led to a rapid and quantitative transformation to a distorted-tetrahedral [Pd4L8] species. On the contrary, [Pd2L4] cages formed from ligands with isoquinoline donors either just encapsulated the guests or showed no interaction. The tetrahedral species could be fully reverted back to its original [Pd2L4] topology by capturing the guest by another, stronger binding [Pd2L′4] coordination cage, narcissistically self-sorting from the first cage. The azulenes, serving as colored hydrocarbon backbones of minimal atom count, allow one to follow cage assembly and guest-induced transformation by the naked eye. Furthermore, we propose that their peculiar electronic structure influences the system’s assembly behavior.

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“…where helicity occurs without torsion restrictions, which is akin 342 to recent work in Pd2L4 cages. 56 Further, we see that there For small ditopic internal angles, removing the torsion re-351 striction has a strong impact, resulting in many low energy 352 cages in the angle map (Fig. S37).…”

Section: Preorganisation Effect On Topology Accessibility So Farmentioning

confidence: 93%

Systematic exploration of accessible topologies of cage molecules via minimalistic models

Tarzia,

Wolpert,

Jelfs

et al. 2023

Preprint

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Cages are macrocyclic structures with an intrinsic internal cavity that support applications in separations, sensing and catalysis. These materials can be synthesised via self-assembly of organic or metal-organic building blocks. Their bottom-up synthesis and the diversity in building block chemistry allows for fine-tuning of their shape and properties toward a target property. However, it is not straightforward to predict the outcome of self-assembly, and, thus, the structures that are practically accessible during synthesis. Indeed, such a prediction becomes more difficult as problems related to the flexibility of the building blocks or increased combinatorics lead to a higher level of complexity and increased computational costs. Molecular models, and their coarse-graining into simplified representations, may be very useful to this end. Here, we develop a minimalistic toy model of cage-like molecules to explore the stable space of different cage topologies based on a few fundamental geometric building block parameters. Our results capture, despite the simplifications of the model, known geometrical design rules in synthetic cage molecules and uncover the role of building block coordination number and preorganisation on the stability of cage topologies. This leads to a large-scale and systematic exploration of design principles, generating data that we expect could be analysed through expandable approaches toward the rational design of self-assembled porous architectures.

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Maximized axial helicity in a Pd₂L₄cage: inverse guest size-dependent compression and mesocate isomerism

Abstract: The extreme axial twist of a Pd2L4 cage facilitates tight encapsulation of mono-anions through prolate-oblate cavity adaptation. In the absence of a suitable guest, the helical cage exists in equilibrium with an ‘unwound’ mesocate isomer.

Cited by 14 publications

References 86 publications

Systematic exploration of accessible topologies of cage molecules via minimalistic models

Systematic exploration of accessible topologies of cage molecules via minimalistic models

Guest-Induced Reversible Transformation between an Azulene-Based Pd₂L₄ Lantern-Shaped Cage and a Pd₄L₈ Tetrahedron

Systematic exploration of accessible topologies of cage molecules via minimalistic models

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Maximized axial helicity in a Pd2L4cage: inverse guest size-dependent compression and mesocate isomerism

Abstract: The extreme axial twist of a Pd2L4 cage facilitates tight encapsulation of mono-anions through prolate-oblate cavity adaptation. In the absence of a suitable guest, the helical cage exists in equilibrium with an ‘unwound’ mesocate isomer.

Cited by 14 publications

References 86 publications

Systematic exploration of accessible topologies of cage molecules via minimalistic models

Systematic exploration of accessible topologies of cage molecules via minimalistic models

Guest-Induced Reversible Transformation between an Azulene-Based Pd2L4 Lantern-Shaped Cage and a Pd4L8 Tetrahedron

Systematic exploration of accessible topologies of cage molecules via minimalistic models

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Maximized axial helicity in a Pd₂L₄cage: inverse guest size-dependent compression and mesocate isomerism

Guest-Induced Reversible Transformation between an Azulene-Based Pd₂L₄ Lantern-Shaped Cage and a Pd₄L₈ Tetrahedron