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rdf:type
lifeskim:mentions
pubmed:issue
40
pubmed:dateCreated
2009-10-7
pubmed:abstractText
We report the application of nanoindentation and atomic force microscopy to establish the fundamental relationships between mechanical properties and chemical bonding in a dense inorganic-organic framework material: Ce(C(2)O(4))(HCO(2)), 1. Compound 1 is a mixed-ligand 3-D hybrid which crystallizes in an orthorhombic space group, in which its three basic building blocks, i.e. the inorganic metal-oxygen-metal (M-O-M) chains and the two organic bridging ligands, (oxalate and formate) are all oriented perpendicular to one another. This unique architecture enabled us to decouple the elastic and plastic mechanical responses along the three primary axes of a single crystal to understand the contribution associated with stiff vs compliant basic building blocks. The (001)-oriented facet that features rigid oxalate ligands down the c-axis exhibits the highest stiffness and hardness (E approximately 78 GPa and H approximately 4.6 GPa). In contrast, the (010)-oriented facet was found to be the most compliant and soft (E approximately 43 GPa and H approximately 3.9 GPa), since the formate ligand, which is the more compliant building block within this framework, constitutes the primary linkages down the b-axis. Notably, intermediate stiffness and hardness (E approximately 52 GPa and H approximately 4.1 GPa) were measured on the (100)-oriented planes. This can be attributed to the Ce-O-Ce chains that zigzag down the a-axis (Ce...Ce metal centers form an angle of approximately 132 degrees) and also the fact that the 9-coordinated CeO(9) polyhedra are expected to be geometrically more compliant. Our results present the first conclusive evidence that the crystal orientation dominated by inorganic chains is not necessarily more robust from the mechanical properties standpoint. Rigid organic bridging ligands (such as oxalate), on the other hand, can be used to produce greater stiffness and hardness properties in a chosen crystallographic orientation. This study demonstrates that there exists a vast opportunity to design the mechanical properties of dense hybrid framework materials through the incorporation of organic multifunctional ligands of varying rigidity.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Oct
pubmed:issn
1520-5126
pubmed:author
pubmed:issnType
Electronic
pubmed:day
14
pubmed:volume
131
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
14252-4
pubmed:year
2009
pubmed:articleTitle
Relating mechanical properties and chemical bonding in an inorganic-organic framework material: a single-crystal nanoindentation study.
pubmed:affiliation
Department of Materials Science and Metallurgy, University of Cambridge, Pembroke Street, Cambridge CB2 3QZ, UK.
pubmed:publicationType
Journal Article