Induced Self-Assembly and Disassembly of Alkynylplatinum(II) 2,6-Bis(benzimidazol-2'-yl)pyridine Complexes with Charge Reversal Properties: "Proof-of-Principle" Demonstration of Ratiometric Förster Resonance Energy Transfer Sensing of pH.

Abstract

A series of pH-responsive alkynylplatinum(II) 2,6-bis(benzimidazol-2'-yl)pyridine (bzimpy) complexes with charge-reversal properties was synthesized, and the supramolecular assemblies between conjugated polyelectrolyte, PFP-OSO3-, and [Pt{bzimpy(TEG)2}{C≡C-C6H3-(COOH)2-3,5}]Cl (1) have been studied using UV-vis absorption, emission, and resonance light scattering (RLS) spectroscopy. An efficient Förster resonance energy transfer (FRET) from PFP-OSO3- donor to the aggregated 1 as acceptor with the aid of Pt(II)···Pt(II) interactions has been presented, which leads to a growth of triplet metal-metal-to-ligand charge transfer (3MMLCT) emission in the low-energy red region. The two-component PFP-OSO3--1 ensemble was then exploited as a "proof-of-principle" concept strategy for pH sensing by tracking the ratiometric emission changes. With the aid of judicious molecular design on the pH-driven charge-reversal property, the polyelectrolyte-induced self-assembly and the FRET from PFP-OSO3- to the platinum(II) aggregates have been modulated. Together with its excellent reversibility and photostability, the extra stability provided by the Pt(II)···Pt(II) and π-π stacking interactions on top of the electrostatic and hydrophobic interactions existing in polyelectrolye-complex assemblies has led to a selective and sensitive pH sensing assay.