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Updated: Mar 12, 2026
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Selective Sensing of Phosphates by a New Bis-heteroleptic RuII Complex through Halogen Bonding: A Superior Sensor
Bijit Chowdhury1, Sanghamitra Sinha1, Pradyut Ghosh1
1Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, 2A&2B Raja S. C. Mullick Road, Kolkata, 700032, India.
Abstract:
The selective phosphate-sensing property of a bis-heteroleptic RuII complex, 1[PF6 ]2 , which has a halogen-bonding iodotriazole unit, is demonstrated and is shown to be superior to its hydrogen-bonding analogue, 2[PF6 ]2 . Complex 1[PF6 ]2 , exploiting halogen-bonding interactions, shows enhanced phosphate recognition in both acetonitrile and aqueous acetonitrile compared with its hydrogen-bonding analogue, owing to considerable amplification of the RuII -center-based metal-to-ligand charge transfer (MLCT) emission response and luminescence lifetime. Detailed solution-state studies reveal a higher association constant, lower limit of detection, and greater change in lifetime for complex 1 in the presence of phosphates compared with its hydrogen-bonding analogue, complex 2. The 1 H NMR titration study with H2 PO4- ascertains that the binding of H2 PO4- occurs exclusively through halogen-bonding or hydrogen-bonding interactions in complexes 1[PF6 ]2 and 2[PF6 ]2 , respectively. Importantly, the single-crystal X-ray structure confirms the first ever report on metal-assisted second-sphere recognition of H2 PO4- and H2 P2 O72- with 1 through a solitary C-I⋅⋅⋅anion halogen-bonding interaction.
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