Synthesis and investigation of donor-porphyrin-acceptor triads with long-lived photo-induced charge-separate states.
Synthesis and investigation of donor-porphyrin-acceptor triads with long-lived photo-induced charge-separate states.
复制标题
供体 - 卟啉-Ceptor-Triad具有长寿命诱导的电荷分离状态的合成和研究。
DOI：
10.1039/c5sc01830g
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发表时间：
2015-11-01
期刊：
影响因子：
8.4
通讯作者：
Anderson HL
中科院分区：
文献类型：
--
作者：
Kelber JB;Panjwani NA;Wu D;Gómez-Bombarelli R;Lovett BW;Morton JJL;Anderson HL
强有力的电子给体四烷基苯二胺（TAPD）促进光诱导电子转移，即使在10 K的冷冻溶剂中，产生长寿命的自旋极化电荷分离态，可以通过EPR观察到。两个供体卟啉受体三联体已被合成使用一个通用的Suzuki偶联路线。这种合成策略允许强有力的供体四烷基苯二胺（TAPD）被引入到基于四芳基卟啉的三单元体中而不需要保护。电子转移的热力学和动力学在新的三单元组相比，与先前报道的ocatalkyldiphenyl卟啉三单元组表现出长寿命的自旋极化电荷分离态（CSS），从理论和实验的角度来看，在流体溶液中，并在冷冻溶剂玻璃。我们表明，四芳基卟啉核心的不利氧化电位可以通过使用C60作为比三蝶烯萘醌（TNQ）更好的电子受体来抵消。C60-卟啉-TAPD三元组给出了一个自旋极化的电荷分离状态，可以通过EPR光谱观察到，在10 K下的平均寿命为16 ms，这比以前报道的TNQ-卟啉-TAPD三元组更长，遵循从计算的电荷重组率预测的趋势。
The powerful electron donor tetraalkylphenylenediamine (TAPD) facilitates photo-induced electron transfer, even in a frozen solvent at 10 K, generating a long-lived spin-polarized charge separate state which can be observed by EPR. Two donor–porphyrin–acceptor triads have been synthesized using a versatile Suzuki-coupling route. This synthetic strategy allows the powerful donor tetraalkylphenylenediamine (TAPD) to be introduced into tetraarylporphyrin-based triads without protection. The thermodynamics and kinetics of electron transfer in the new triads are compared with a previously reported octaalkyldiphenyl-porphyrin triad exhibiting a long-lived spin-polarized charge separate state (CSS), from theoretical and experimental perspectives, in both fluid solution and in a frozen solvent glass. We show that the less favorable oxidation potential of the tetraaryl-porphyrin core can be offset by using C60, as a better electron-acceptor than triptycenenaphthoquinone (TNQ). The C60–porphyrin–TAPD triad gives a spin-polarized charge-separated state that can be observed by EPR-spectroscopy, with a mean lifetime of 16 ms at 10 K, which is longer than in the previously reported TNQ–porphyrin–TAPD triad, following the predicted trend from calculated charge-recombination rates.