Source:http://linkedlifedata.com/resource/pubmed/id/18855358
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| Predicate | Object |
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| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
45
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| pubmed:dateCreated |
2008-11-6
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| pubmed:abstractText |
Two new bis-bidentate bridging ligands have been prepared, L (naph) and L (anth), which contain two chelating pyrazolyl-pyridine units connected to an aromatic spacer (naphthalene-1,5-diyl and anthracene-9,10-diyl respectively) via methylene connectors. Each of these reacts with transition metal dications having a preference for octahedral coordination geometry to afford {M 8L 12} (16+) cages (for L (anth), M = Cu, Zn; for L (naph), M = Co, Ni, Cd) which have an approximately cubic arrangement of metal ions with a bridging ligand spanning each of the twelve edges, and a large central cavity containing a mixture of anions and/or solvent molecules. The cages based on L (anth) have two cyclic helical {M 4L 4} faces, of opposite chirality, connected by four additional L (anth) ligands as "pillars"; all metal centers have a meridional tris-chelate configuration. In contrast the cages based on L (naph) have (noncrystallographic) S 6 symmetry, with a diagonally opposite pair of corners having a facial tris-chelate configuration with the other six being meridional. An additional significant difference between the two types of structure is that the cubes containing L (anth) do not show significant interligand aromatic stacking interactions. However, in the cages based on L (naph), there are six five-membered stacks of aromatic ligand fragments around the periphery, each based on an alternating array of electron-rich (naphthyl) and electron-deficient (pyrazolyl-pyridine, coordinated to M (2+)) aromatic units. A consequence of this is that the cages {M 8(L (naph)) 12} (16+) retain their structural integrity in polar solvents, in contrast to the cages {M 8(L (anth)) 12} (16+) which dissociate in polar solvents. Consequently, the cages {M 8(L (naph)) 12} (16+) give NMR spectra in agreement with the symmetry observed in the solid state, and their fluorescence spectra (for M = Cd) display (in addition to the normal naphthalene-based pi-pi* fluorescence) a lower-energy exciplex-like emission feature associated with a naphthyl --> pyrazolyl-pyridine charge-transfer excited state arising from the pi-stacking between ligands around the cage periphery.
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:month |
Nov
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| pubmed:issn |
1520-5126
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| pubmed:author | |
| pubmed:issnType |
Electronic
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| pubmed:day |
12
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| pubmed:volume |
130
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| pubmed:owner |
NLM
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| pubmed:authorsComplete |
Y
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| pubmed:pagination |
15167-75
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| pubmed:year |
2008
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| pubmed:articleTitle |
Octanuclear cubic coordination cages.
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| pubmed:affiliation |
Department of Chemistry, University of Sheffield, UK.
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| pubmed:publicationType |
Journal Article
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