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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Using Three-Pulse Femtosecond Spectroscopy to Probe Ultrafast Triplet Energy Transfer in Zinc meso-Tetraarylporphyrin-Perylene-3,4-dicarboximide Dyads
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Using Three-Pulse Femtosecond Spectroscopy to Probe Ultrafast Triplet Energy Transfer in Zinc meso-Tetraarylporphyrin-Perylene-3,4-dicarboximide Dyads

机译：使用三脉冲飞秒光谱探测内消旋-四芳基卟啉-Per-3,4-二甲酰亚胺亚胺中的超快三重态能量转移

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摘要

Linear arrays of zinc meso-tetraarylporphyrin (ZnP), perylene-3,4-dicarboximide (PMI), and either naphthalene-1,8:4,5-bis(dicarboximide) (NI) or pyromellitimide (PI) were synthesized and studied by ultrafast transient absorption spectroscopy. PMI was covalently linked in one of two orientations relative to ZnP. In one set of molecules, the 9 position of the perylene core is connected to the para position of a meso-phenyl in ZnP to give ZnP-PMI-N-X, where X = NI or PI is attached to the imide nitrogen atom of PMI. In the second set of compounds, the imide nitrogen atom of PMI is connected to the meso-phenyl in ZnP to give ZnP-N-PMI-X, where X = PI or H. Selective excitation of ZnP using 420 nm, 110 fs laser pulses in each molecule in toluene produces ~(1~*)ZnP, which intersystem crosses (ISC) to ~(3~*)ZnP with τ = 2.3 ns. For ZnP-PMI-N-X, triplet energy transfer (TET) from ~(3~*)ZnP to PMI is much faster than ISC, so that ~(3~*)ZnP is not observed by one-pump-one-probe transient absorption spectroscopy. Following its formation, the lowest excited triplet state of ~(3~*)PMI was excited with a 575 nm, 110 fs laser pulse to produce an upper excited triplet state, ~(3~(**))PMI. In ZnP-PMI-N-X, subpicosecond TET from ~(3~(**))PMI re-populates ~(3~*)ZnP, which subsequently undergoes TET back to PMI with a rate of (7 ps)~(-1). The same experiment carried out on ZnP-N-PMI-X reveals that the TET process ~(3~*)ZnP-N-PMI-X ZnP-~(3*)N-PMI-X occurs with a rate of (55 ns)-1. The nearly 8000-fold larger TET rate from ~(3~*)ZnP to PMI in ZnP-PMI-N-X relative to that in ZnP-N-PMI-X is a consequence of the larger -orbital coefficients at the 9 position in both the HOMO and LUMO of PMI relative to that on its imide nitrogen atom. This basic asymmetry allows optimization of energy and electron and/or hole transfer rates in large assemblies containing PMI for use in organic molecular electronics.
机译：合成并研究了内消旋四芳基卟啉锌（ZnP），per 3,4-二苯甲酰亚胺（PMI）和萘1,8：4,5-双（二苯甲酰亚胺）（NI）或均苯四甲酰亚胺（PI）的线性阵列通过超快速瞬态吸收光谱法。 PMI以相对于ZnP的两个方向之一共价连接。在一组分子中，the核的9位与ZnP中内消旋苯基的对位连接，得到ZnP-PMI-N-X，其中X = NI或PI连接至PMI的酰亚胺氮原子。在第二组化合物中，PMI的酰亚胺氮原子与ZnP中的内消旋苯基相连，得到ZnP-N-PMI-X，其中X = PI或H。使用420 nm，110 fs激光选择性激发ZnP甲苯中每个分子中的脉冲产生〜（1〜*）ZnP，系统间穿过（ISC）到〜（3〜*）ZnP，τ= 2.3 ns。对于ZnP-PMI-NX，从〜（3〜*）ZnP到PMI的三重态能量转移（TET）比ISC快得多，因此在一泵一探针瞬态中未观察到〜（3〜*）ZnP吸收光谱。形成后，〜（3〜*）PMI的最低激发三重态被575 nm，110 fs激光脉冲激发，产生了一个较高的激发三重态〜（3〜（**））PMI。在ZnP-PMI-NX中，来自〜（3〜（**））PMI的亚皮秒TET会重新填充〜（3〜*）ZnP，其随后以（7 ps）〜（-1）的速率经过TET返回PMI ）。对ZnP-N-PMI-X进行的同一实验表明，TET过程〜（3〜*）ZnP-N-PMI-X ZnP-〜（3 *）N-PMI-X的发生速率为（55 ns）-1。相对于ZnP-N-PMI-X，从ZnP-PMI-NX的〜（3〜*）ZnP到PMI的TET速率大将近8000倍，这是两个位置的9位轨道系数更大的结果相对于酰亚胺氮原子上的PMI的HOMO和LUMO。这种基本的不对称性可以优化用于有机分子电子产品的包含PMI的大型组件中的能量，电子和/或空穴传输速率。

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