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Allosteric Manipulation of Photoexcited State Relaxation in a Series of Ru II (bpy) 2 (bipyridine−crown ethers)
Author(s) -
Dutta Subodh K.,
Gan Daqing,
Perkovic Marc W.
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200200654
Subject(s) - chemistry , ruthenium , bipyridine , crown ether , luminescence , pyridine , 2,2' bipyridine , crystallography , 4,4' bipyridine , allosteric regulation , photochemistry , stereochemistry , ion , medicinal chemistry , crystal structure , molecule , organic chemistry , hydrogen bond , catalysis , enzyme , optoelectronics , physics
A series of ruthenium( II ) crown ether complexes containing 4‐, 5‐, or 6‐oxygen crowns tethered to a bipyridine at the 3,3′ position were prepared and examined for their ability to act as luminescent sensors. The complexes [(bpy) 2 Ru(2,2′‐bipyridine‐3,3′‐16‐crown‐4)](PF 6 ) 2 and [(bpy) 2 Ru(2,2′‐bipyridine‐3,3′‐19‐crown‐5)](PF 6 ) 2 were characterized by X‐ray crystallography. The 4‐oxygen crown crystallizes in the P $\bar 1$ space group. The 5‐oxygen crown crystallizes in the P $\bar 1$ space group. In both complexes, the inter‐pyridine ring angle in the tethered bipyridine is twisted substantially away from 0°. Coordination of a heavy metal ion such as Pb 2+ by the crown ether, and the geometric changes that result, were examined by UV/Vis, luminescence and NMR spectroscopy. The results show that there is a weak allosteric interaction between the Pb 2+ ion and the Ru complexes, and that this interaction alters the luminescent behavior of the Ru complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)