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

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• 作者：Che-Jen Lin ; Chih-Yuan Chen ; Sandip Kumar Kundu ; Jye-Shane Yang
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：January 21, 2014
• 年：2014
• 卷：53
• 期：2
• 页码：737-745
• 全文大小：451K
• ISSN：1520-510X

文摘

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鈥?02 渭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鈥?% 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 700 渭s), leading to an 鈥渙n鈥搊ff鈥?optical response to oxygen concentration. Both the dual emissive properties and long-lived triplet excitons are attributed to diminished spin鈥搊rbit couplings caused by twisting and steric shielding of the 蟺-conjugated backbone around the Pt center.