Inorganic Chemistry, Vol.55, No.1, 259-271, 2016
A Cyanuric Acid Platform Based Tripodal Bis-heteroleptic Ru(II) Complex of Click Generated Ligand for Selective Sensing of Phosphates via C-H center dot center dot center dot Anion Interaction
A new bis-heteroleptic trinudear Ru(II) complex (1[PF6](6)) has been synthesized from electron deficient cyanuric acid platform based copper-catalyzed azide alkyne cydoaddition, i.e., CuAAC click generated ligand, 1,3,5-tris [(2-aminoethyl-1H-1,2,3-triazol-4-yl)-pyridine]-1,3,5-triazinane-2,4,6-trione (L1). Complex 1[PF6]6 displays weak luminescence (phi(f) = 0.002) at room temperature with a short lifetime of 5 ns in acetonitrile. It shows selective sensing of hydrogen pyrophosphate (HP2O73-) through 20-fold enhanced emission intensity (phi(f) = 0.039) with a 15 nm red shift in emission maxima even in the presence of a large excess of various competitive anions like F-, Cl-, AcO-, BzO(-), NO3-, HCO3-, HSO4-, HO-, and H2PO4- in acetonitrile. Selective change in the decay profile as well as in the lifetime of 1[PF6](6) in the presence of HP2O73- (108 ns) further supports its selectivity toward HP2O73-. UV vis and photoluminescence titration profiles and corresponding Job's plot analyses suggest 1:3 host guest stoichiometric binding between 1[PF6](6) and HP2O73-. High emission enhancement of 1[PF6](6) in the presence of HP2O73- has resulted in the detection limit of the anion being as low as 0.02 mu M. However, 1[PF6](6) shows selectivity toward higher analogues of phosphates (e.g., ATP, ADP, and AMP) over HP2O73-/H2PO4- in 10% Tris HCl buffer (10 mM)/acetonitrile medium. Downfield shifting of the triazole C-H in a H-1 NMR titration study confirms that the binding of HP2O73-/H2PO4- is occurring via C-H center dot center dot center dot anion interaction. The single crystal X-ray structure of complex 1 having NO3- counteranion, 1[NO3](6) shows binding of NO3- with complex 1 via C-H center dot center dot center dot NO3- interactions.