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Steering the Shape-shifting of Bullvalene-PdII Complexes Through Steric and Geometric Strain

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dc.contributor.authorBirvé, A.P.
dc.contributor.authorBloch, W.M.
dc.contributor.authorFallon, T.
dc.date.issued2026
dc.description.abstractDi-substituted bullvalenes are fluxional molecules possessing up to fifteen possible isomers. Their shape-shifting nature has been harnessed in host-guest chemistry, drug design, polymers, and electromechanical systems. Despite this, principles for controlling the fluxional pathways of bullvalene, including access to isomers that are not normally populated, remain poorly understood. In this study, we elucidate the restricted shapeshifting of bis-pyridyl bullvalene ligands in ethylenediamine (en) cis-capped PdII complexes. The energetic landscape of 3-substituted bis-pyridyl bullvalene remains open to A and B isomers in [Pd2(en)L2] complexes, whilst the coordination of 4- and 2-substituted bis-pyridyl derivatives significantly restrict bullvalene's isomerization pathway. In one case, chelation of bis-2-pyridyl bullvalene enables access to an otherwise energetically inaccessible D-isomer. Exclusive formation of this isomer is achieved by increasing the sterics of the cis-capping ligand.
dc.description.statementofresponsibilityAndré P. Birvé, Witold M. Bloch, and Thomas Fallon
dc.identifier.citationAngewandte Chemie International Edition, 2026; 65(16):e23441-1-e23441-7
dc.identifier.doi10.1002/anie.202523441
dc.identifier.issn1433-7851
dc.identifier.issn1521-3773
dc.identifier.orcidBloch, W.M. [0000-0003-1084-1287]
dc.identifier.orcidFallon, T. [0000-0002-6495-5282]
dc.identifier.urihttps://hdl.handle.net/2440/150050
dc.language.isoen
dc.publisherWiley
dc.relation.granthttp://purl.org/au-research/grants/arc/DP250103453
dc.relation.granthttp://purl.org/au-research/grants/arc/FT240100330
dc.rights© 2026 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License
dc.source.urihttps://doi.org/10.1002/anie.202523441
dc.subjectCoordination modes
dc.subjectFluxionality
dc.subjectSelf‐assembly
dc.subjectValence isomerization
dc.titleSteering the Shape-shifting of Bullvalene-PdII Complexes Through Steric and Geometric Strain
dc.typeJournal article
pubs.publication-statusPublished

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