Induced Self-Assembly of Platinum(II) Alkynyl Complexes through Specific Interactions between Citrate and Guanidinium for Proofof-Principle Detection of Citrate and an Assay of Citrate Lyase

Water-soluble alkynylplatinum(II) terpyridine complexes appended with guanidinium moieties, [Pt(tpy)(C Ar)][OTf](2) (tpy = terpyridine; OTf = trifluoromethanesulfonate; Ar=C6H4-{NHC(=NH(2)e)(NH2(+))}-4 (1), C6H4-{CH2NHC(= NH2+)(NH2)}-4 (2)), and [Pt(tBu3tpy)(CCC6H4-{NHC(= NH2+)(NH2)}-4)1[OTf](2) (3; tBu3tpy=4,4',4 ''-tri-tert-butyl-2,2':6n2 ''-terpyridine), have been synthesized and characterized. The photophysical properties of the complexes have been studied. Based on the results of UVNis absorption, resonance light scattering, and dynamic light scattering experiments, in aqueous buffer solutions complexes 1 and 2 undergo aggregation in the presence of citrate through strong and specific electrostatic and hydrogen-bonding interactions with citrate. The emergence of a triplet metal-metal-to- ligand charge transfer (3MMLCT) emission in the near-infrared (NIR) region brought on by the induced self-assembly of complex 1 has been demonstrated for proof-of-principle detection of citrate with good sensitivity and selectivity over other mono- and dicarboxylate substrates in the tricarboxylic acid (TCA) cycle as well as phosphate and lactate anions. Such a good selectivity toward citrate has been rationalized by the high charge density of citrate under physiological conditions and specific interactions between the guanidinium moiety on complex 1 and citrate. Extension of the work to citrate detection in fetal bovine serum and real-time monitoring of the activity of citrate lyase by the NIR emission of complex 1 have also been demonstrated.