Chiral Self‐Sorting in Pd<sub>6</sub>L<sub>12</sub> Metal‐Organic Cages

Ghorai, Sandipan; Maji, Suman; Paul, Bhaswati; Samanta, Krishanu; Sen, Shovan Kumar; Natarajan, Ramalingam

doi:10.1002/asia.202201312

Cited by 6 publications

(3 citation statements)

References 41 publications

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“…86 Such screening could also exploit another tool to direct the crystal packing in molecular materials: chiral recognition. [87][88][89][90][91] Cooper and co-workers invoked the possibility of chiral recognition to achieve the capsule head-to-head motif on the unsubstituted isotrianglimine. 21 Therefore, we explored the use of heterochiral co-crystallisation of bromo-isotrianglimine to investigate the effect on both the polymorphs obtained and the macrocycles present in the structure.…”

Section: Figure 6: (A) Schematic Showing the Crystallisation Conditio...mentioning

confidence: 99%

Dynamic and solid-state behaviour of bromoisotrianglimine

Scholes,

Kershaw-Cook,

Szczypiński

et al. 2023

Preprint

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Solid-state materials formed from discrete imine macrocycles have potential in industrial separations, but dynamic behaviour during both synthesis and crystallisation makes them challenging to exploit. Here, we explore opportunities for structural control by investigating the dynamic nature of a C-5 brominated isotrianglimine in solution and under crystallisation conditions. In solution, the equilibrium between the [3+3] and the less reported [2+2] macrocycle was investigated, and both macrocycles were fully characterised. Solvent templating during crystallisation was used to form new packing motifs for the [3+3] macrocycle and an unreported [4+4] macrocycle. Finally, chiral self-sorting was used to demonstrate how crystallisation conditions can not only influence packing arrangements but also shift the macrocycle equilibrium to yield new structures. This work thus exemplifies three strategies for exploiting dynamic behaviour to form isotrianglimine materials, and highlights the importance of understanding the dynamic behaviour of a system when designing and crystallising functional materials formed using dynamic covalent chemistry.

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Section: Figure 6: (A) Schematic Showing the Crystallisation Conditio...mentioning

confidence: 99%

Dynamic and solid-state behaviour of bromoisotrianglimine

Scholes,

Kershaw-Cook,

Szczypiński

et al. 2023

Preprint

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“…The most commonly used counter ions in synthesis of metal macrocyclic complexes are PF 6 − , BF 4 − , CF 3 SO 3 − , NO 3 − , BPh 4 − , etc. [49][50][51][52]…”

Section: Use Of Seed Crystals and Effect Of Counter Ionsmentioning

confidence: 99%

Step‐By‐Step Tips to Grow X‐Ray Quality Single Crystals of Metal Macrocyclic Complexes

Gupta

Lee

2023

Cryst. Res. Technol.

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Metal macrocyclic complexes, which are formed through a self-assembly process due to the presence of several coordinating sites in the metal and ligand source, represent an interesting class of complexes due to their intriguing structures and functionalities. Although spectral characterization of metal macrocyclic complexes is reported, elucidation of their exact structure at the molecular level remains challenging. Single-crystal X-ray diffraction (SCXRD) is a non-destructive analytical technique that can provide detailed information about the internal lattice of crystalline structure. However, it requires the growth of single crystals of suitable sizes and quality. This study provides an overview of methods that are most useful for developing single crystals of metal macrocyclic complexes, particularly when the macrocycle of interest is present in extremely low quantities (a few milligrams). The reproducibility of previous methods reporting the crystal growth of different metal macrocycles is also investigated. A review highlighting and summarizing the most common tips to grow single crystals for metal macrocyclic complexes can help in understanding and optimizing the growth of crystals suitable for SCXRD.

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“…The synthesis of enantiopure chiral cages has received significant interest due to their potential applications in asymmetric catalysis, [34][35][36] recognition of chiral guest molecules, [37][38][39][40][41] enantioselective sensing, [42] etc. Although, synthesis of chiral coordination cages from achiral subunits mostly yields a racemic mixture of both enantiomers, [43] several strategies have led to enantiopure cages through chiral induction or resolution from enantiomeric pairs. [41,[44][45][46] Mukherjee and colleagues explored the phenomena of reverse chiral recognition in an octahedral coordination cage, demonstrating that the chirality of the guest molecule can determine the handedness of the host, leading to enantiopure assembly.…”

Section: Introductionmentioning

confidence: 99%

Chiral Induction in a Self‐Assembled Pd₄ Coordination Cage with Chiral Guests

Singha,

Maity,

Samanta

2024

Chemistry A European J

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The dynamic interplay of coordination bonds within metal‐organic cages offers a unique avenue for structural evolution in response to external stimuli, presenting a promising strategy for the construction of chiral assemblies. This adaptability is crucial for the selective synthesis of homochiral assemblies and advancement of asymmetric catalysis. In this study, we report the self‐assembly of an achiral square‐planar Pd(II) acceptor with a C2‐symmetric tetrapyridyl donor resulted in the formation of a racemic mixture of the chiral octahedral cage Pd4L2. The existence of this racemic mixture was confirmed using circular dichroism spectroscopy as well as single crystal X‐ray diffraction analysis. We encoded chiral information into the asymmetric cavity of the cage by encapsulating chiral aromatic guests through efficient π‐π stacking and hydrophobic interactions in aqueous media. The inclusion of a chiral guest induces a preference for one enantiomeric conformation of the cage over the other, effectively shifting the equilibrium towards a single, enantiopure host‐guest complex. While the concept of chiral guest recognition by a chiral host is well‐established, this work constitutes a remarkable example of guest‐mediated chirality transfer leading to the formation of a single enantiopure coordination complex from achiral building blocks.

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Chiral Self‐Sorting in Pd₆L₁₂ Metal‐Organic Cages

Cited by 6 publications

References 41 publications

Dynamic and solid-state behaviour of bromoisotrianglimine

Dynamic and solid-state behaviour of bromoisotrianglimine

Step‐By‐Step Tips to Grow X‐Ray Quality Single Crystals of Metal Macrocyclic Complexes

Chiral Induction in a Self‐Assembled Pd₄ Coordination Cage with Chiral Guests

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Chiral Self‐Sorting in Pd6L12 Metal‐Organic Cages

Cited by 6 publications

References 41 publications

Dynamic and solid-state behaviour of bromoisotrianglimine

Dynamic and solid-state behaviour of bromoisotrianglimine

Step‐By‐Step Tips to Grow X‐Ray Quality Single Crystals of Metal Macrocyclic Complexes

Chiral Induction in a Self‐Assembled Pd4 Coordination Cage with Chiral Guests

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Chiral Self‐Sorting in Pd₆L₁₂ Metal‐Organic Cages

Chiral Induction in a Self‐Assembled Pd₄ Coordination Cage with Chiral Guests