Unichromophoric Platinum-Acetylides That Contain Pentiptycene Scaffolds: Torsion-Induced Dual Emission and Steric Shielding of Dynamic Quenching

作者：Lin Che Jen; Chen Chih Yuan; Kundu Sandip Kumar; Yang Jye Shane^*

来源：Inorganic Chemistry, 2014, 53(2): 737-745.

DOI：10.1021/ic4025052

The effect of the rigid bulky pentiptycene scaffolds on the photoluminescence, redox properties, and oxygen sensing behavior of unichromophoric Pt-acetylides is reported. When the pentiptycene groups are near the Pt(PBu3)(2) center, the Pt-acetylides display both blue fluorescence and green phosphorescence with long phosphorescence lifetimes (90-202 mu s) in THF. Their phosphorescence intensity is highly sensitive to molecular oxygen, and the emission color depends on the concentration of not only oxygen but also the complexes, which allows a feasible determination of oxygen in the range of 1-5% air volume. The dynamic quenching rate constants decrease linearly with increasing the number of pentiptycene groups, revealing the steric shielding effect of the peripheral rings of pentiptycene. A dependence of oxidation potential on the number of pentiptycene groups also revealed the steric shielding effect on the electron transfer between the complexes and the electrode. In a PMMA matrix, the dual emissive properties are diminished due to increased phosphorescence and decreased fluorescence intensity, and the phosphorescence lifetimes are significantly increased (up to similar to 700 mu s), leading to an "on-off" optical response to oxygen concentration. Both the dual emissive properties and long-lived triplet excitons are attributed to diminished spin-orbit couplings caused by twisting and steric shielding of the if-conjugated backbone around the Pt center.

• 出版日期2014-1-20