Cyclometalated Platinum(II) Terpyridylacetylide with a Bis(arylamine) Donor as a Proton-Triggered Luminescence Chemosensor for Zn(2+).

Abstract

A cyclometalated Pt(II) acetylide derivative bearing a bis(arylamine) donor (D) and a terpyridine (TPY) receptor (A) was successfully synthesized and characterized. This three-component D-π-A system displays an intense low-energy absorption band at λmax = 470 nm, resulting from overlapping the dπ(Pt) → π*(C^N^N) metal-to-ligand charge transfer and π(C≡C-Ar) → π*(C^N^N) ligand-to-ligand charge transfer transitions with the π(bis(arylamine)) → π*(C^N^N) intraligand charge transfer transition. Upon protonation of the bis(arylamine) donor, a strong emission from the phosphorescence Pt(II) complex unit is recovered at λmax = 580 nm. With introduction of the TPY receptor, this complex possesses quite high affinity for Zn(2+) (Ka = 6.86 × 10(9) mol(-2)·dm(6)) to form the heterotrinuclear Pt-Zn-Pt complex in CH2Cl2 solution. Though this coordination effect is seriously inhibited by protons in acidic medium, the 2.4-fold luminescence intensity enhancement is obtained yet, strongly suggesting the presence of the intramolecular energy transfer process from the Zn(II)-TPY complex core to the phosphorescence Pt(II) complex units at two ends. The H(+)-triggered and Zn(2+)-enhanced luminescence can be reversibly switched on and off upon successive additions of H(+) and OH(-). Furthermore, this complex displays an unexpected Zn(2+)-selective luminescence enhancement effect in acidic solution.