On the relation of energy and electron transfer in multidimensional chromophores based on polychlorinated triphenylmethyl radicals and triarylamines.
On the relation of energy and electron transfer in multidimensional chromophores based on polychlorinated triphenylmethyl radicals and triarylamines.
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DOI：
10.1039/c4cp05929h
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发表时间：
2015-04
期刊：
影响因子：
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通讯作者：
M. Steeger;Stefanie Griesbeck;A. Schmiedel;M. Holzapfel;Ivo Krummenacher;H. Braunschweig;C. Lambert
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文献类型：
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作者：
M. Steeger;Stefanie Griesbeck;A. Schmiedel;M. Holzapfel;Ivo Krummenacher;H. Braunschweig;C. Lambert
合成了一种星型化合物，该化合物由三个三芳胺（TAA）和三个三芳胺（TAA）分别取代的对称和不对称六芳苯（HAB）与多氯三苯甲基（PCTM）组成。在星状化合物的氧化还原中心之间的强通信观察到电子顺磁共振光谱和UV/维斯/NIR吸收测量，而在HABs只有一个弱的相互作用可以检测到。通过超快瞬态吸收测量监测激发态的时间演化。在第一皮秒稳定的电荷转移状态观察到诱导溶剂旋转。各向异性瞬态吸收测量表明，在激发态（τ = 1-4 ps）的寿命内，能量转移不会发生在HAB中，而在类星系统中观察到超快和可能相干的能量再分布。把这些信息结合起来，我们就可以明显地看出特定系统中能量转移和电子转移之间的同一性。
A star-like compound consisting of a polychlorinated triphenylmethyl radical (PCTM) core linked to three triarylamines (TAA) and a symmetric and an asymmetric hexaarylbenzene (HAB) both substituted with three PCTMs and three TAAs were synthesised. In the star-like compound a strong communication between the redox centres was observed by electron paramagnetic resonance spectroscopy and UV/Vis/NIR absorption measurements, whereas in the HABs only a weak interaction could be detected. The temporal evolution of the excited states was monitored by ultrafast transient absorption measurements. Within the first picosecond stabilisation of the charge transfer state was observed induced by solvent rotation. Anisotropic transient absorption measurements revealed that within the lifetime of the excited state (τ = 1-4 ps) energy transfer does not occur in the HABs whereas in the star-like system ultrafast and possibly coherent energy redistribution is observed. Taken this information together we made the identity between energy transfer and electron transfer in the specific systems apparent.