Selective recognition and sensing of biologically and environmentally important anions especially phosphates are very challenging task due to their high solvation energies (Ghyd of H2PO4− ≈ –465 kJ/mol; (Ghyd of PO43− ≈ –2765 kJ/mol). A series of seven bis-heteroleptic Ru(II) probes (1[PF6]2 -9[PF6]2) containing similar anion binding triazole unit (hydrogen bond donor) functionalized with varieties of substituents are employed for a detailed comparative investigation for the development of superior selective probes for H2PO4. Various solution and solid state studies, such as 1H-DOSY NMR, Dynamic Light Scattering (DLS), Single Crystal X-ray Crystallography, and Transmission Electron Microscope (TEM) have established that the selective sensing of H2PO4 by this series of probes are primarily due to supramolecular aggregation driven enhancement of 3MLCT emission. Interestingly, 1[PF6]2 and 7[PF6]2 ¬having a pentafluorophenyl electron-deficient (π-acidic) aromatic substituent are found to be the superior probes for H2PO4 as compared to other aryl and polyaromatic substituted analogs (2[PF6]2 -6[PF6]2, 8[PF6]2 and 9[PF6]2), in terms of higher enhancement of 3MLCT emission band, greater binding constant, and lower detection limit. Superiority of 1[PF6]2 and 7[PF6]2 could be due to better supramolecular aggregation property in cases of pentafluorophenyl analogs via both hydrogen bonding and anion-fluorine / anion- non-covalent interactions

Influence of Triazole Substituents of Bis-Heteroleptic Ru(II) Probes toward Selective Sensing of Dihydrogen Phosphate

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27th CRSI National Symposium in Chemistry

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