Variations on a Cage Theme: Some Complexes of Bicyclic Polyamines as Supramolecular Synthons

Ian J. Clark; Alessandra Crispini; Paul S. Donnelly; Lutz M. Engelhardt; Jack M. Harrowfield; Seong-Hoon Jeong; Yang Kim; George A. Koutsantonis; Young Hoon Lee; Nigel A. Lengkeek; Mauro Mocerino; Gareth L. Nealon; Mark I. Ogden; Yu Chul Park; Claudio Pettinari; Lara Polanzan; Elisabeth Rukmini; Alan M. Sargeson; Brian W. Skelton; Alexandre N. Sobolev; Pierre Thuéry; Allan H. White

doi:10.1071/CH09356

RESEARCH FRONT

Variations on a Cage Theme: Some Complexes of Bicyclic Polyamines as Supramolecular Synthons

Ian J. Clark ^A , Alessandra Crispini ^B , Paul S. Donnelly ^A , Lutz M. Engelhardt ^A , Jack M. Harrowfield ^A ^C ^K , Seong-Hoon Jeong ^D , Yang Kim ^D , George A. Koutsantonis ^A , Young Hoon Lee ^E , Nigel A. Lengkeek ^A , Mauro Mocerino ^F , Gareth L. Nealon ^A , Mark I. Ogden ^F , Yu Chul Park ^E , Claudio Pettinari ^G , Lara Polanzan ^G , Elisabeth Rukmini ^H , Alan M. Sargeson ^I , Brian W. Skelton ^A , Alexandre N. Sobolev ^A , Pierre Thuéry ^J and Allan H. White ^A

+ Author Affiliations

- Author Affiliations

^A Chemistry M313, School of Biomedical and Chemical Sciences, University of Western Australia, Crawley, WA 6009, Australia.

^B Centro di Eccellenza CEMIF.CAL-LASCAMM, CR-INSTM (Unità della Calabria, Dipartimento di Chimica), Dipartimento di Scienze Farmaceutiche, Edificio Polifunzionale, Università della Calabria, I-87030 Arcavacata di Rende (CS), Italy.

^C Current address: Institut de Science et d’Ingénierie Supramoléculaires, Université de Strasbourg, 67083 Strasbourg, France.

^D Department of Advanced Materials, Kosin University, 149-1, Dongsam-dong, Yeongdo-gu, Busan, 606-701, Korea.

^E Department of Chemistry, Kyungpook National University, Daegu, 702-701, Korea.

^F Nanochemistry Research Institute, Department of Applied Chemistry, Curtin University of Technology, Bentley, WA 6845, Australia.

^G Chemical Sciences Department, University of Camerino, 62032 Camerino MC, Italy.

^H Chemistry Unit, Faculty of Medicine, Atma Jaya Catholic University, Jakarta 14440, Indonesia.

^I (Deceased) Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia.

^J CEA, ARAMIS, SIS2M, LCCEf (CNRS URA 331), Bâtiment 125, 91191 Gif-sur-Yvette, France.

^K Corresponding author. Email: harrowfield@isis.u-strasbg.fr

Australian Journal of Chemistry 62(10) 1246-1260 https://doi.org/10.1071/CH09356
Submitted: 22 June 2009 Accepted: 3 August 2009 Published: 13 October 2009

Abstract

Dedication: One of Alan Sargeson’s great abilities was to seek out knowledge on topics of which he was not the master from those people with the expertise. This led occasionally to publications with a ‘cricket team’ of authors but with a rich brew of information, often international. Alan also insisted that all authors were equal since, without any one, the paper would not be what it was. Hence, he endeavoured to pursue the policy, difficult to maintain over a period where an obsession with absurdities such as the order of authors and point-scoring based on meaningless publication indices became so important in the maintenance of research, of listing authors simply in alphabetical order. In describing work begun while he was still with us, we have attempted to adhere to his principles.

Analysis of a body of crystallographic information concerning metal(ii) and metal(iii) complexes of macrobicyclic hexamine ligands and some of their derivatives provides evidence for the action of a variety of intermolecular forces within the lattices. Hydrogen bonding is universal and its forms depend strongly upon the oxidation state and the particular nature of the metal ion bound to the macrobicycle. The introduction of both aliphatic and aromatic substituents leads to lattices in which these substituents associate, although, in the case of aromatic substituents, this is not necessarily a consequence of ‘π-stacking’, despite the fact that the aromatic ring planes form parallel arrays. At least in the case of Co^III, stable enantiomers of the complexes can be obtained, and in {Δ-(+)₅₈₉-[Co{(NH₃)(CH₃)sar}]}₂Cl₂(C₆(CO₂)₆)·26H₂O (sar = 3,6,10,13,16,19-hexa-azabicyclo[6.6.6]icosane), the benzene hexacarboxylate anion adopts a chiral conformation in the presence of the optically active cation.

Acknowledgements

This work was supported by Kosin University and (in part) by the Australian Research Council.

References

Variations on a Cage Theme: Some Complexes of Bicyclic Polyamines as Supramolecular Synthons

Abstract

Acknowledgements

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