~(99)Ru and ~(13)C-NMR Spectra for the Tris Chelates of 5-Substituted 1,10-Phenanthrolines with Ruthenium (Ⅱ)

Ru(5-X-Phen),' complexes(whereX=H,CH3,Ph,Cl,andNO2)havebeenfoundtohaveextensiveapplicationascatalystsinphotoinducedelectron-transferprocessesand,especially,asphotosensitizersinsolarenergyconversionbywaterphotoreductionprocesses.Someresearchersincludingthepresentauthorhavefound1Handl3CNMRspectroscopyusefultostudytheinteractionsthatdevelopincoordinationofpolypyridineligandstotransitionmetalsl-3.Sincethe99Ru-NMRchendcalshiftcansensitivelyreflecttheelectronicandgeometricalchangesaroundtheme…     

(Strept)avidin as host for biotinylated coordination complexes: stability, chiral discrimination, and cooperativity

Incorporation of a biotinylated ruthenium tris(bipyridine) [Ru(bpy)(2)(Biot-bpy)](2+) (1) in either avidin or streptavidin-(strept)avidin-can be conveniently followed by circular dichroism spectroscopy. To determine the stepwise association constants, cooperativity, and chiral discrimination properties, diastereopure (Lambda and Delta)-1 species were synthesized and incorporated in tetrameric (strept)avidin to afford (Delta-[Ru(bpy)(2)(Biot-bpy)](2+))(x)() subsetavidin, (Lambda-[Ru(bpy)(2)(Biot-bpy)](2+))(x)() subsetavidin, (Delta-[Ru(bpy)(2)(Biot-bpy)](2+))(x)() subsetstreptavidin, and (Lambda-[Ru(bpy)(2)(Biot-bpy)](2+))(x)() subsetstreptavidin (x = 1-4) For these four systems, the overall stability constants are log beta(4) = 28.6, 30.3, 36.2, and 36.4, respectively. Critical analysis of the CD titrations data suggests a strong cooperativity between the first and the second binding event (x = 1, 2) and a pronounced difference in affinity between avidin and streptavidin for the dicationic guest 1 as well as modest enantiodiscrimination properties with avidin as host.