Quenching of triplet states of organic compounds by copper(II) and nickel(II) 1,3-diketonates in acetonitrile solution. Energy and/or electron transfer
Quenching of triplet states of organic compounds by copper(II) and nickel(II) 1,3-diketonates in acetonitrile solution. Energy and/or electron transfer
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DOI：
10.1021/j100082a022
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发表时间：
1994-08
期刊：
影响因子：
--
通讯作者：
G. Hug;B. Marciniak
中科院分区：
文献类型：
--
作者：
G. Hug;B. Marciniak
Cu（II）bis对15种有机化合物三重态猝灭的速率常数（2，4-戊二酮）、Cu（acac）[sub 2]、铜（II）双（1，1，1，5，5，5-六氟-2，4-戊二酮）、Cu（hfac）[sub 2]、Ni（II）bis用纳秒激光闪光光解技术测量了乙腈溶液中的Ni（2，4-戊二酮）（Ni（acac）[sub 2]）和Ni（II）双（1，1，1，5，5，5-六氟-2，4-戊二酮）（Ni（hfac）[sub 2]）。猝灭数据被解释为能量或电子转移单独或两者作为竞争过程。与一个经典的能量和电子转移的框架，淬火速率常数与标准的能量和电子转移的自由能变化的相关性被用来评估适当的内在障碍和传输系数为这两个过程。在乙腈中，Cu（acac）[sub 2]的猝灭主要通过电子转移发生，而Cu（hfac）[sub 2]的猝灭则涉及到与电子转移相结合的配体定位三重态的能量转移。参考文献58篇，图4，5片。
Rate constants for quenching of the triplet states of 15 organic compounds by copper(II) bis(2,4-pentanedionate), Cu(acac)[sub 2], copper(II) bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate), Cu(hfac)[sub 2], Ni(II) bis(2,4-pentanedionate), Ni(acac)[sub 2], and Ni(II) bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate), Ni(hfac)[sub 2], in acetonitrile solution have been measured using the nanosecond laser flash photolysis technique. The quenching data were interpreted in terms of energy or electron transfer alone or in terms of both as competitive processes. With a classical framework for energy and electron transfer, the correlations of the quenching rate constants with the standard free energy changes for energy and electron transfer were used to evaluate appropriate intrinsic barriers and transmission coefficients for both processes. In acetonitrile, quenching by Cu(acac)[sub 2] was suggested to occur mainly by electron transfer, whereas quenching by Cu(hfac)[sub 2] was shown to involve energy transfer to the ligand-localized triplet in combination with electron transfer. 58 refs., 4 figs., 5 tabs.