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首页> 外文期刊>Chemistry: A European journal >Efficient Intramolecular Charge Transfer in Oligoyne-Linked Donor–p–Acceptor Molecules
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Efficient Intramolecular Charge Transfer in Oligoyne-Linked Donor–p–Acceptor Molecules

机译：Oligoyne连接的供体-p-受体分子的高效分子内电荷转移。

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Studies are reported on a eries of triphenylamine–(CC)n–2,5- diphenyl-1,3,4-oxadiazole dyad molecules (n=1–4, 1, 2, 3 and 4, respectively) and the related triphenylamine-C6H4–(CC)3–xadiazole dyad 5. The oligoyne-linked D–p–A (D=electron donor, A=electron acceptor) dyad systems have been synthesised by palladium- catalysed cross-coupling of terminal alkynyl and butadiynyl synthons with the corresponding bromoalkynyl moieties. Cyclic voltammetric studiesreveal a reduction in the HOMO–LUMO gap in the series of compounds1–4 as the oligoyne chain length increases,which is consistent with extended conjugation through the elongated bridges. Photophysical studies provide new insights into conjugative effects in oligoyne molecular wires. In non-polar solvents the emission from thes dyad systems has two different origi ns: a locally excited (LE) state,which is responsible for a p*!p fluorescence,and an ntramolecular charge transfer (ICT) state, which produces charge-transfer emission. In polar solvents the LE state emission vanishes and only ICT emission is observed.This emission displays strong ochromism and analysis according to the Lippert–Mataga–Oshika formalism shows significant ICT for all the luminescent compounds with high efficiency even for the longer more conjugated systems. The excited-state operties of the dyads in non-polar solvents vary with the extent of conjugation. For more conjugated systems a fast non-radiative route dominates the excitedstate decay and follows the Engelman–Jortner energ gap law. The data suggest that the non-radiative decay is driven by the weak oupling limit.
机译：有关三苯胺–（CC）n–2,5-二苯基-1,3,4-恶二唑二元分子（分别为n = 1–4、1、2、3和4）和相关的三苯胺的研究报道-C6H4–（CC）3–二唑二联体5。寡聚炔连接的D–p–A（D =电子供体，A =电子受体）二联体系是通过钯催化末端炔基和丁二炔基合成子的交叉偶联而合成的。与相应的溴炔基部分。循环伏安法研究表明，随着低聚炔链长度的增加，一系列化合物1-4中HOMO-LUMO间隙的减小，这与通过细长桥的扩展共轭相符。光物理研究为寡聚分子丝的共轭作用提供了新的见解。在非极性溶剂中，二元体系的发射具有两个不同的起源：局部激发（LE）状态和ap荧光;以及分子间电荷转移（ICT）状态，产生电荷转移。排放。在极性溶剂中，LE态发射消失，仅观察到ICT发射。根据Lippert-Mataga-Oshika形式主义的分析，该发射显示出强烈的变色现象，对所有发光化合物而言，即使对于更长的共轭体系，其ICT也具有很高的效率。在非极性溶剂中二元体的激发态操作随共轭程度而变化。对于更多的共轭系统，快速的非辐射路径主导着激发态的衰变，并遵循Engelman–Jortner能隙定律。数据表明，非辐射衰减是由弱耦合极限驱动的。

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