Diastereoselectively self-sorted low-symmetry binuclear metallomacrocycle and trinuclear metallocage

Mishra, Srabani Srotoswini; Chand, Dillip Kumar

doi:10.1039/d2dt01571d

Cited by 13 publications

(6 citation statements)

References 33 publications

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“…Symmetric, dipyridyl analogues of these ditopic ligands [26] have been shown to assemble into ‘double‐walled’ Pd 3 L 6 triangles (Figure 5b). [36,37] For such structures assembled from an unsymmetrical ligand, one instance of which has been reported by Chand and co‐workers, [38] there are 9 possible isomers. Two of these provide all‐ cis or all‐ trans arrangements of donors at the three metal nodes (Figure 5b).…”

Section: Resultsmentioning

confidence: 98%

Diastereoselective Self‐Assembly of Low‐Symmetry Pd_nL_2n Nanocages through Coordination‐Sphere Engineering**

Molinska,

Tarzia,

Male

et al. 2023

Angewandte Chemie

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Metal‐organic cages (MOCs) are popular host architectures assembled from ligands and metal ions/nodes. Assembling structurally complex, low‐symmetry MOCs with anisotropic cavities can be limited by the formation of statistical isomer libraries. We set out to investigate the use of primary coordination‐sphere engineering (CSE) to bias isomer selectivity within homo‐ and heteroleptic PdnL2n cages. Unexpected differences in selectivities between alternative donor groups led us to recognise the significant impact of the second coordination sphere on isomer stabilities. From this, molecular‐level insight into the origins of selectivity between cis and trans diastereoisomers was gained, highlighting the importance of both host‐guest and host‐solvent interactions, in addition to ligand design. This detailed understanding allows precision engineering of low‐symmetry MOC assemblies without wholesale redesign of the ligand framework, and fundamentally provides a theoretical scaffold for the development of stimuli‐responsive, shape‐shifting MOCs.

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Section: Resultsmentioning

confidence: 98%

Diastereoselective Self‐Assembly of Low‐Symmetry Pd_nL_2n Nanocages through Coordination‐Sphere Engineering**

Molinska,

Tarzia,

Male

et al. 2023

Angewandte Chemie

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“…But the “ cis rule” seems to be more general. The available experimental results for [Pd n L 2 n ] 2 n + assemblies based on low-symmetry ligands show that there is also a bias for the formation of “ cis complexes” in the case of lantern-shaped cages ( n = 2), , trinuclear macrocycles ( n = 3), , tetrahedral cages ( n = 4), and cuboctahedral cages ( n = 12) . From a purely geometric point-of-view, a high degree of orientational self-sorting is expected for ligands with a pronounced “degree of asymmetry”.…”

Section: Discussionmentioning

confidence: 99%

Orientational Self-Sorting in Octahedral Palladium Cages: Scope and Limitations of the “cis Rule”

de Montmollin,

Solea,

Chen

et al. 2024

Inorg. Chem.

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Octahedral coordination cages of the general formula [Pd 6 L 12 ](BF 4 ) 12 were obtained by combining [Pd(CH 3 CN) 4 ](BF 4 ) 2 with heteroditopic N-donor ligands. Four different ligands were employed. These ligands have 3-pyridyl donor groups at one end and 4-pyridyl, imidazolyl, or triazolyl donor groups at the other end. According to a geometric analysis, cages with a cis configuration at the six metal centers should be preferred ("cis rule"). This prediction was corroborated by spectroscopic data and crystallographic analyses. Limitations of the "cis rule" were also encountered, and possible explanations are discussed.

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“…5b). 35,36 For such structures assembled from an unsymmetrical ligand, one instance of which has been reported by Chand and co-workers, 37 there are 9 possible isomers. Two of these provide all-cis or all-trans arrangements of donors at the three metal nodes (Fig.…”

Section: Pd3l6 'Double-walled' Trianglesmentioning

confidence: 94%

Diastereoselective self-assembly of low-symmetry PdnL2n nanocages through coordination-sphere engineering

Molinska,

Tarzia,

Male

et al. 2023

Preprint

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Metal-organic cages (MOCs) are popular host architectures assembled from ligands and metal ions/nodes. Assembling structurally complex, low-symmetry MOCs with anisotropic cavities can be limited by the formation of statistical isomeric libraries. We set out to investigate the use of primary coordination-sphere engineering (CSE) to bias diastereoselectivity within homo- and heteroleptic PdnL2n cages. Unexpected differences in stereoselectivity between alternative donor groups led us to recognise the significant impact of the second coordination sphere on isomer stabilities. From this, molecular-level insight into the origins of the diastereoselectivity was gained, highlighting the importance of both host-guest and host-solvent interactions, in addition to ligand design. This detailed understanding allows precision engineering of low-symmetry MOC assemblies without wholesale redesign of the ligand framework, and fundamentally provides a theoretical scaffold for the development of stimuli-responsive, shape-shifting MOCs.

show abstract

Diastereoselectively self-sorted low-symmetry binuclear metallomacrocycle and trinuclear metallocage

Abstract: A pyridine/aniline appended unsymmetrical bis-monodentate ligand N-(3-aminophenyl)nicotinamide, Lun is synthesized by condensation of nicotinic acid with excess of m-phenylene diamine. Low-symmetry binuclear complex of Pd2L'2Lun2 type and extremely rare trinuclear...

Cited by 13 publications

References 33 publications

Diastereoselective Self‐Assembly of Low‐Symmetry Pd_nL_2n Nanocages through Coordination‐Sphere Engineering**

Diastereoselective Self‐Assembly of Low‐Symmetry Pd_nL_2n Nanocages through Coordination‐Sphere Engineering**

Orientational Self-Sorting in Octahedral Palladium Cages: Scope and Limitations of the “cis Rule”

Diastereoselective self-assembly of low-symmetry PdnL2n nanocages through coordination-sphere engineering

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Diastereoselectively self-sorted low-symmetry binuclear metallomacrocycle and trinuclear metallocage

Abstract: A pyridine/aniline appended unsymmetrical bis-monodentate ligand N-(3-aminophenyl)nicotinamide, Lun is synthesized by condensation of nicotinic acid with excess of m-phenylene diamine. Low-symmetry binuclear complex of Pd2L'2Lun2 type and extremely rare trinuclear...

Cited by 13 publications

References 33 publications

Diastereoselective Self‐Assembly of Low‐Symmetry PdnL2n Nanocages through Coordination‐Sphere Engineering**

Diastereoselective Self‐Assembly of Low‐Symmetry PdnL2n Nanocages through Coordination‐Sphere Engineering**

Orientational Self-Sorting in Octahedral Palladium Cages: Scope and Limitations of the “cis Rule”

Diastereoselective self-assembly of low-symmetry PdnL2n nanocages through coordination-sphere engineering

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Diastereoselective Self‐Assembly of Low‐Symmetry Pd_nL_2n Nanocages through Coordination‐Sphere Engineering**

Diastereoselective Self‐Assembly of Low‐Symmetry Pd_nL_2n Nanocages through Coordination‐Sphere Engineering**