Electrochemiluminescence Properties of [Pt2Ag4(C鈮C6H4R)8]n (R = CH3, n = 1; R = H, n = 1 and 2) with

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• 作者：Qiao-Hua Wei ; Li-Jing Han ; Yi Jiang ; Xiao-Xia Lin ; Ya-Nan Duan ; Guo-Nan Chen
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：October 15, 2012
• 年：2012
• 卷：51
• 期：20
• 页码：11117-11125
• 全文大小：499K
• 年卷期：v.51,no.20(October 15, 2012)
• ISSN：1520-510X

文摘

Two hexanuclear clusters, [Pt₂Ag₄(C鈮C₆H₄R)₈] (R = CH₃, 1; R = H, 2), together with dimer [Pt₂Ag₄(C鈮C₆H₅)₈]₂ (3), have been synthesized and characterized by elemental analyses, electrospray ionization mass spectrometry, and ¹H NMR spectroscopy and by X-ray crystallography for 1 and 3. A considerable enhancement of photoluminescence (PL) and a notable red shift in the emission maximum of 1 (位_max 600 nm) relative to 2 (位_max 545 nm) are observed. Electrogenerated chemiluminescence (ECL) of 1 and 2 in the absence or presence of coreactant tri-n-propylamine (TPrA) or 2-(dibutylamino)ethanol (DBAE) at different working electrodes in different solvents (CH₂Cl₂, CH₂ClCH₂Cl, or CH₃CN) has been studied. The ECL spectra are identical with the PL spectra, indicating that ECL emissions are also due to a MLM鈥睠T [Pt(d)/蟺 (C鈮C₆H₄R-4) 鈫?Pt(p_z)/Ag(sp)/蟺* (C鈮C₆H₄R-4)] state modified by Pt路路路Ag and Ag路路路Ag contacts. ECL of 1- and 2/amine systems in CH₂ClCH₂Cl was produced at the potentials of 1.14鈥?.19 V vs SCE, notably negatively shifted by about 0.38 V compared to those of the Ru(bpy)₃²⁺/amine system. In all cases, ECL quantum efficiencies of 2 are higher than those of 1 and on the same order of magnitude as that of the [Ru(bpy)₃](PF₆)₂/amine system. It is noted that Sudan I tends to decrease the ECL intensity of the 1/DBAE system in CH₂ClCH₂Cl at a platinum working electrode. A new ECL method for the determination of Sudan I was developed with a linear range of 2.5 脳 10^鈥?鈥?.0 脳 10^鈥? M and a detection limit of 8.0 脳 10^鈥? M based on 3 times the ratio of signal-to-noise.