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Shaping and enforcing coordination spheres: Probing the ability of tripodal ligands to favour trigonal prismatic geometry

Lookup NU author(s): Dr James KnightORCiD



This is the authors' accepted manuscript of an article that has been published in its final definitive form by Royal Society of Chemistry, 2016.

For re-use rights please refer to the publisher's terms and conditions.


© 2016 The Royal Society of Chemistry.We report two tripodal frameworks, mono(2,2′-bipyrid-6-yl)bis(2-pyridyl)methanol (L1) and bis(2,2′-bipyrid-6-yl)mono(2-pyridyl)methanol (L2) which have one and two bipyridyl arms, respectively. Both ligands form complexes with the first row transition metals. Both ligands appear to overcome the steric strain involved in twisting the ligand to produce an octahedral complex and the solid state structures in general show more octahedral character than complexes of the related ligand, tris(2,2′-bipyrid-6-yl)methanol (L3). Continuous Shape Mapping (CShM) calculations based on crystallographic data reveal that L1 is incapable of enforcing a trigonal prismatic (TP) co-ordination geometry in the solid state, surprisingly even upon co-ordination to metals with no stereochemical preference such as cadmium (S(TP) = 7.15 and S(Oh) = 3.95). However, ligand L2 clearly maintains an ability to enforce a trigonal prismatic conformation which is demonstrated in the crystal structures of the MnII and CdII complexes (S(TP) = 0.75 and 1.09, respectively). While L3 maintains near-TP configurations in the presence of metal ions with strong octahedral preferences, L2 distorts towards predominantly octahedral co-ordination geometries, increasing in the order CoII < NiII < FeII and no trigonal prismatic structures.

Publication metadata

Author(s): Knight JC, Amoroso AJ, Edwards PG, Singh N, Ward BD

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2016

Volume: 45

Issue: 26

Pages: 10630-10642

Print publication date: 14/07/2016

Online publication date: 31/05/2016

Acceptance date: 28/05/2016

Date deposited: 30/08/2018

ISSN (print): 1477-9226

ISSN (electronic): 1477-9234

Publisher: Royal Society of Chemistry


DOI: 10.1039/c6dt01165a


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