ISMSC 2007 - Università degli Studi di Pavia

Neutral supramolecular systems incorporating bis--diketonat metallocyclic
building blocks: a remarkable reversible single crystal-singol crystal bond
breaking/bond forming transformation under pressure.
Jack K. Clegg a , Katrina A. Jolliffe b , Leonard F. Lindoy, a Simon Parsons, c David Schilter, b Peter
Tasker c and Fraser J. White. c
a
Centre for Heavy Metals Research, School of Chemistry, F11, University of Sydney, NSW,
Australia, 2006.
b
School of Chemistry, F11, University of Sydney, NSW, Australia, 2006.
c
Centre for Science at Extreme Conditions and School of Chemistry, King’s Buildings,
University of Edinburgh, West Mains Road, Edinburgh, Scotland, EH9 3JJ
The interaction of a variety of aryl-linked bis--diketones with cobalt(II), nickel(II), copper(II),
zinc(II), gallium(III), iron(III) and zirconium(IV) has been investigated with the aim of obtaining
new metallo-supramolecular assemblies. New binuclear, trinuclear and tetranuclear assemblies
have been shown to form in a variety of geometries including helical, co-bifacial, triangular and
tetrahedral arrangements that reflect the directional properties of the ligand and the metal
ion.[1-2]
In particular, the use of copper(II) leads to the formation of neutral dinuclear and trinuclear
species containing coordinatively unsaturated metal centres. These can then be reacted with
nitrogen-containing ligands to form extended ‘linked’ structures including discrete ‘dimers of
dimers’ and a variety of 1D, 2D and 3D network solids.[3-4]
When using 1-methylpiperazine as a ‘linking’ ligand a one dimensional chain polymer results (I).
When a single crystal of this complex is loaded into a diamond anvil cell and the pressure
increased, a fully reversible chemical reaction occurs. The structure transforms from a polymer
to a discrete dimeric species (II). This transformation is accompanied by a phase change from
triclinic to monoclinic. This is the first such example of a reversible pressure induced singlecrystal
to single-crystal chemical reaction yet reported.
[1] D. J. Bray, J. K. Clegg, L. F. Lindoy, D. Schilter, Adv. Inorg. Chem., 2006, 59, 1-39
[2] J. K. Clegg, D.J. Bray, K. Gloe, K. Gloe, M. J. Hayter, K. A. Jolliffe, G. A. Lawrance, G. V.
Meehan, J. C. McMurtrie, L. F. Lindoy, and M. Wenzel, Dalton Trans., 2007, in press.
[3] J. K. Clegg, Aust. J. Chem. 2006, 59, 660;
[4] J. K. Clegg, K. Gloe, M. J. Hayter, O. Kataeva, L. F. Lindoy, B. Moubaraki, J. C.
McMurtrie, K. S. Murray and D. Schilter, Dalton Trans., 2006, 3977;
PSA 29
A ditopic biomimetic receptor : role of the 1 st , 2 nd and 3 rd coordination
spheres.
D. Coquière a , T. Prangé b , J. Marrot c , B. Colasson a , O. Reinaud a .
PSA 30
a Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601,
Université René Descartes, 45 rue des Saints-Pères, 75270 Paris cedex 06, France
b Laboratoire de Cristallographie, UMR CNRS 8015, Université René Descartes, 4 avenue de
l’Observatoire, 75270 Paris cedex 06, France
c Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles St-Quentin en
Yvelines, 45 av. des Etats-Unis, 78035 Versailles cedex, France
Calix[6]arenes are superb molecular platforms offering a -basic hydrophobic cavity that can act
as a selective receptor for a variety of molecules. For such a case, only the cone conformation
of the calixarene is able to act as a molecular host. We have extensively described a system
that presents a biomimetic tris-imidazole core at the small rim [1]. This system allows efficient
binding of a metal ion such as Zn(II) that acts as a glue, fixing at the same time three aromatic
units of the calixarene core. As a result, the tetrahedral complex behaves as a remarkable
receptor for small exogenous neutral ligands.
Recently, we have discovered efficient methods allowing the selective functionalization of the
calixarene large rim [2, 3]. This opened the possibility of synthesizing ditopic calixarene ligands.
Here, the coordination chemistry and the host-guest properties of a calix[6]arene containing a
nitrogenous binding site at each rim are presented [4].
Zn(II)-monometallic complex (left) hosting a dopamine derivative and Zn(II)-bimetallic complex
(right) encapsulating H302 - .
[1] O. Sénèque, M.-N. Rager, M. Giorgi and O. Reinaud, J. Am. Chem. Soc., 2001, 123, 8442.
[2] S. Redon, Y. Li and O. Reinaud, J. Org. Chem., 2003, 68, 7004.
[3] D. Coquière, H. Cadeau, Y. Rondelez, M. Giorgi and O. Reinaud, J. Org. Chem., 2006, 71,
4059.
[4] D. Coquière, J. Marrot and O. Reinaud, Chem. Commun., 2006, 3924.