A Springloaded Metal-Ligand Mesocate Allows Access to Trapped Intermediates of Self-Assembly

Bogie, Paul M.; Holloway, Lauren R.; Lyon, Yana A.; Onishi, Nicole; Beran, Gregory J. O.; Julian, Ryan R.; Hooley, Richard J.

doi:10.1021/acs.inorgchem.8b00370

Cited by 19 publications

(11 citation statements)

References 69 publications

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“…This generates two binding modes: convex (θ ≈ 90°) with nitrogen donors pointing away from the substituent(s), and concave (θ ≈ 40°) pointing in the same direction (Scheme S4). A similar backbone design was reported to lead to Fe-based helicates and tetrahedra, − as well as knots and Borromean rings …”

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confidence: 74%

Integrative Assembly of Heteroleptic Tetrahedra Controlled by Backbone Steric Bulk

et al. 2021

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A bent fluorenone-based dipyridyl ligand L A reacts with Pd II cations to a solvent-dependent dynamic library of [Pd n L 2 n ] assemblies, constituted by a [Pd 3 L A 6 ] ring and a [Pd 4 L A 8 ] tetrahedron as major components, and a [Pd 6 L A 12 ] octahedron as minor component. Introduction of backbone steric hindrance in ligand L B allows exclusive formation of the [Pd 6 L B 12 ] octahedron. Combining equimolar amounts of both ligands results in integrative self-sorting to give an unprecedented [Pd 4 L A 4 L B 4 ] heteroleptic tetrahedron. Key to the non-statistical assembly outcome is exploiting the structural peculiarity of the [Pd 4 L 8 ] tetrahedral topology, where the four lean ligands occupy two doubly bridged edges and the bulky ligands span the four remaining, singly bridged edges. Hence, the system finds a compromise between the entropic drive to form an assembly smaller than the octahedron and the enthalpic prohibition of pairing two bulky ligands on the same edge of the triangular ring. The emission of luminescent L A is maintained in both homoleptic [Pd 3 L A 6 ] and heteroleptic [Pd 4 L A 4 L B 4 ].

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confidence: 74%

Integrative Assembly of Heteroleptic Tetrahedra Controlled by Backbone Steric Bulk

et al. 2021

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“…Our 'solution' did not actually end up being a solution, but it is an interesting idea: Can we use a metastable helicate such as the xanthone cage 10 as starting material? 63 Adding diamine ligands to 10 showed some extremely unusual selfassembly behavior. Depending on the nature of diamine, multiple different reaction outcomes could be observed that were independent of the nucleophilicity of the diamine and were instead completely dominated by the stability of the assembly.…”

Section: Syn Lettmentioning

confidence: 99%

“…The various outcomes are far too many to be described here, but the reader is directed to ref. 63 for a full account, with apologies for its length. One quick illustration of the large differences in reactivity between highly similar ligands is shown in Scheme 8.…”

Section: Syn Lettmentioning

confidence: 99%

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No, Not That Way, the Other Way: Creating Active Sites in Self-Assembled Host Molecules

Hooley¹

2020

Synlett

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This Account describes our efforts over the last decade to synthesize self-assembled metal–ligand cage complexes that display reactive functional groups on their interiors. This journey has taken us down a variety of research avenues, including studying the mechanism of reversible self-assembly, analyzing ligand self-sorting properties, post-assembly reactivity, molecular recognition, and binding studies, and finally reactivity and catalysis. Each of these individual topics are discussed here, as are the lessons learned along the way and the future research outlook. These self-assembled hosts are the closest mimics of enzymes to date, as they are capable of size- and shape-selective molecular recognition, substrate activation and turnover, as well as showing less common ‘biomimetic’ properties such as the ability to employ cofactors in reactivity, and alter the prevailing mechanism of the catalyzed reactions.1 Introduction2 Paddlewheels and Self-Sorting Behavior3 First-Row Transition-Metal-Mediated Assembly: Sorting and Stereochemical Control4 Post-Assembly Reactivity5 Molecular Recognition and Catalysis6 Conclusions and Outlook

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“…Reports of the self-assembly of metallo-supramolecular structures under nonequilibrium conditions remain rare. 8−10…”

Section: Introductionmentioning

confidence: 99%

Probing the Dynamics of the Imine-Based Pentafoil Knot and Pentameric Circular Helicate Assembly

et al. 2019

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We investigate the self-assembly dynamics of an imine-based pentafoil knot and related pentameric circular helicates, each derived from a common bis(formylpyridine)bipyridyl building block, iron(II) chloride, and either monoamines or a diamine. The mixing of circular helicates derived from different amines led to the complete exchange of the N-alkyl residues on the periphery of the metallo-supramolecular scaffolds over 4 days in DMSO at 60 °C. Under similar conditions, deuterium-labeled and nonlabeled building blocks showed full dialdehyde building block exchange over 13 days for open circular helicates but was much slower for the analogous closed-loop pentafoil knot (>60 days). Although both knots and open circular helicates self-assemble under thermodynamic control given sufficiently long reaction times, this is significantly longer than the time taken to afford the maximum product yield (2 days). Highly effective error correction occurs during the synthesis of imine-based pentafoil molecular knots and pentameric circular helicates despite, in practice, the systems not operating under full thermodynamic control.

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A Springloaded Metal-Ligand Mesocate Allows Access to Trapped Intermediates of Self-Assembly

Cited by 19 publications

References 69 publications

Integrative Assembly of Heteroleptic Tetrahedra Controlled by Backbone Steric Bulk

Integrative Assembly of Heteroleptic Tetrahedra Controlled by Backbone Steric Bulk

No, Not That Way, the Other Way: Creating Active Sites in Self-Assembled Host Molecules

Probing the Dynamics of the Imine-Based Pentafoil Knot and Pentameric Circular Helicate Assembly

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