Electrogenerated Chemiluminescence of Platinum(II) Alkynyl Terpyridine Complex with Peroxydisulfate as Coreactant

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• 作者：Zuofeng Chen ; Keith Man-Chung Wong ; Eric Chi-Ho Kwok ; Nianyong Zhu ; Yanbing Zu ; Vivian Wing-Wah Yam
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：March 21, 2011
• 年：2011
• 卷：50
• 期：6
• 页码：2125-2132
• 全文大小：955K
• 年卷期：v.50,no.6(March 21, 2011)
• ISSN：1520-510X

文摘

A Pt(II) alkynyl terpyridine complex containing a carbazole moiety, [Pt(^tBu₃tpy)(C鈮鈭扖₆H₄-4-carbazole-9)]⁺ (^tBu₃tpy = 4,4鈥?4鈥测€?tri-tert-butyl-2,2鈥?6鈥?2鈥测€?terpyridine) 1, has been synthesized and characterized. The photophysical behavior has been studied, and the molecular structure has been determined by X-ray crystallography. The complex was found to exhibit intense electrogenerated chemiluminescence (ECL) using peroxydisulfate (S₂O₈^{2鈭?/sup>) as coreactant in acetonitrile/water (1鈭?5%, v/v) mixture at both glassy carbon and gold electrodes, representing the first ECL example of the Pt(II) alkynyl family. The ECL was produced at potential corresponding to the first reduction wave (鈭?.90 V vs SCE), significantly shifted by 0.65 V toward more positive potential compared with that of [Ru(bpy)₃]2+ (bpy = 2,2鈥?bipyridine). The ECL spectrum was found to be identical to the photoluminescence spectrum recorded in the same medium, indicating the formation of the same excited state of d蟺(Pt) 鈫?蟺*(tBu₃tpy) 3MLCT mixed with 蟺(C鈮R) 鈫?蟺*(tBu₃tpy) 3LLCT in both cases. The ECL mechanism was proposed involving the formation of the strongly oxidizing intermediate, SO₄鈥⑩垝, mainly generated during the catalytic reduction of S₂O₈2鈭?/sup> by the electrogenerated 1鈭?/sup>. Chemiluminescence of 1/S₂O₈2鈭?/sup> based on reduction with Al metal is also described.}