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首页> 外文期刊>The journal of physical chemistry, C. Nanomaterials and interfaces >Nitro End Groups: Remarkable Vibrational Reporters for Charge Transfer in the Excited States of Oligo(p-phenyleneethynylene)-Bridged Donor-Acceptor Dyads
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Nitro End Groups: Remarkable Vibrational Reporters for Charge Transfer in the Excited States of Oligo(p-phenyleneethynylene)-Bridged Donor-Acceptor Dyads

机译：硝基端组：在寡核苷酸（对亚苯基乙烯）的激发态中的电荷转移的显着振动记者 - 曾经的供体 - 受体二元

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The D-pi-A dyads [(n-Hex)(2)N(1,4-C6H4)]C C[(1,4-C6H4)NO2] (1) and [(n-Hex)(2)N(1,4-C6H4)]C C(1,4-C6H4)C C[(1,4-C6H4)NO2] (2) have been studied by ultrafast time-resolved infrared absorption spectroscopy. After excitation into their singlet charge-transfer ((CT)-C-1) state, a fast decay (ca. 6 ps for 1 and 1 ps for 2) of the initially populated singlet state into a ground state (major pathway) and a longer lived excited state (possibly the triplet state) is observed. The nitro and alkyne groups were used as vibrational reporters to probe the changes induced by the charge-transfer process. For the first time, we confirm experimentally that these changes are consistent with expectations based on the traditional valence-bond representations of the CT states of these push-pull chromophores. An almost identical charge transfer takes place in the two dyads, despite pi-bridges of different lengths between the donor and acceptor groups. Complementary DFT calculations support the experimental assignments and have helped clarify the photophysical behavior of 1 and 2.
机译：D-PI-A二元[（N-Hex）（2）N（1,4-C6H4）] CC [（1,4-C6H4）NO2]（1）和[（N-HEX）（2）n （1,4-C6H4）] CC（1,4-C6H4）CC [（1,4-C6H4）NO2]（2）已经通过超快时间分辨的红外吸收光谱进行研究。在激发到它们的单线时电荷转移（（CT）-C-1）状态后，将最初填充的单线态的快速衰减（约1ps为1ps，1 ps，1 ps，2）到地面状态（主要途径）和观察到更长的兴奋状态（可能是三重态）。硝基和炔基团被用作振动记者，以探测电荷转移过程引起的变化。我们首次证实，这些变化与基于这些推拉发色团的CT态的传统价键表示的期望一致。尽管供体和受体基团之间的不同长度的Pi桥，但在两种二元时，几乎相同的电荷转移发生。互补的DFT计算支持实验任务，并有助于澄清1和2的光物理行为。

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