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Supramolecular selection in molecular alloys

Bouzaid, Jocelyne, Schultz, Madeleine, Lao, Zane, Bartley, John, Bostrom, Thor, & McMurtrie, John (2012) Supramolecular selection in molecular alloys. Crystal Growth and Design, 12(8), pp. 3906-3916.

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Abstract

Complexes of the type M(phen)32 (M = Ni(II), Fe(II), Ru(II) and phen = 1,10-phenanthroline) were found to co-crystallize to form molecular alloys (solid solutions of molecules) with general formula MAxMB1–x(phen)32·0.5H2O in which the relative concentrations of the metal complexes in the crystals closely match those in the crystallizing solution. Consequently, the composition of the co-crystals can be accurately predicted and controlled by modulating the relative concentrations of the metal complexes in the crystallizing solution. Although they are chemically and structurally similar, complexes of the type M(bipy)32 (M = Ni(II), Fe(II), Ru(II) and bipy = 2,2′-bipyridine) display markedly different behavior upon co-crystallization. In this case, the resulting co-crystals of general formula MAxMB1–x(bipy)32 have relative concentrations of the constituent complexes that are markedly different from the relative concentrations of the complexes initially present in the crystallizing solution. For example, when the nickel and iron complexes are co-crystallized from a solution containing a 50:50 ratio of each, the result is the formation of some crystals with a higher proportion of iron and others with a higher proportion of nickel. The relative concentrations of the metal complexes in the crystals can vary from those in the crystallizing solutions by as much as 15%. This result was observed for a range of combinations of metal complexes (Ni/Fe, Ni/Ru, and Fe/Ru) and a range of starting concentrations in the crystallizing solutions (90:10 through to 10:90 in 10% increments). To explain this remarkable result, we introduce the concept of “supramolecular selection”, which is a process driven by molecular recognition that leads to the partially selective aggregation of like molecules during crystallization.

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ID Code: 54355
Item Type: Journal Article
Keywords: Co-crystallisation, Molecular alloys, Supramolecular selection, Molecular recognition
DOI: 10.1021/cg300320r
ISSN: 1528-7483
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > MACROMOLECULAR AND MATERIALS CHEMISTRY (030300) > Nanochemistry and Supramolecular Chemistry (030302)
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 29 Oct 2012 08:42
Last Modified: 13 Jun 2013 01:15

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