Generation of phosphorescent triplet states via photoinduced electron transfer: energy and electron transfer dynamics in Pt porphyrin-Rhodamine B dyads.
Generation of phosphorescent triplet states via photoinduced electron transfer: energy and electron transfer dynamics in Pt porphyrin-Rhodamine B dyads.
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DOI：
10.1021/jp301345h
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发表时间：
2012-04-12
影响因子：
2.9
通讯作者：
Vinogradov, Sergei A.
中科院分区：
文献类型：
--
作者：
Mani, Tomoyasu;Niedzwiedzki, Dariusz M.;Vinogradov, Sergei A.
对激发电子态的产生和动力学的控制是它们在所有技术领域中的应用的基础。我们提出了第一个例子的多发色团系统中，发射三重态是通过涉及光诱导电子转移（ET）的途径，而不是本地intrachromophoric过程。在PtP-Phn-pRh B+（1-3，n=1-3）模型二元体中，PtP和罗丹明B哌嗪衍生物（pRh B+）通过低聚对亚苯基桥（Phn）连接，当pRh B+在低于PtP最低允许跃迁的频率下被选择性激发时，观察到PtP的室温T1→ S 0磷光。导致发射性PtP三重态的途径包括pRhB+的激发、ET与单线态自由基对的形成、该对内的系间交叉和随后的自由基重组。由于PtP和pRhB+的三重态能级非常接近，在二联体1和2中观察到这些状态之间的可逆三重态-三重态（TT）能量转移。结果，PtP的磷光通过pRhB+三重态的长衰变而在时间上延长。在同一系列分子中观察到ET和TT使得能够直接比较这两个密切相关的过程之间的距离衰减因子β。
Control over generation and dynamics of excited electronic states is fundamental to their utilization in all areas of technology. We present the first example of multichromophoric systems in which emissive triplet states are generated via a pathway involving photoinduced electron transfer (ET), as opposed to local intrachromophoric processes. In model dyads, PtP-Phn-pRhB+ (1-3, n=1-3), comprising platinum(II) meso-tetraarylporphyrin (PtP) and rhodamine B piperazine derivative (pRhB+), linked by oligo-p-phenylene bridges (Phn), upon selective excitation of pRhB+ at a frequency below that of the lowest allowed transition of PtP, room-temperature T1→S0 phosphorescence of PtP was observed. The pathway leading to the emissive PtP triplet state includes excitation of pRhB+, ET with formation of the singlet radical pair, intersystem crossing within that pair and subsequent radical recombination. Due to the close proximity of the triplet energy levels of PtP and pRhB+, reversible triplet-triplet (TT) energy transfer between these states was observed in dyads 1 and 2. As a result, the phosphorescence of PtP was extended in time by the long decay of the pRhB+ triplet. Observation of ET and TT in the same series of molecules enabled direct comparison of the distance attenuation factors β between these two closely related processes.
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影响因子：
3.6
作者：
Apreleva, SV;Wilson, DE;Vinogradov, SA
通讯作者：
Vinogradov, SA
影响因子：
8.6
作者：
Graham, Kenneth R.;Yang, Yixing;Reynolds, John R.
通讯作者：
Reynolds, John R.
影响因子：
1.4
作者：
EASTWOOD, D;GOUTERMA.M
通讯作者：
GOUTERMA.M
影响因子：
15
作者：
Holmes, Andrea E.;Das, Debasis;Canary, James W.
通讯作者：
Canary, James W.
影响因子：
1.6
作者：
Araki, N;Obata, M;Yano, S
通讯作者：
Yano, S