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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Restricted photochemistry in the molecular solid state: Structural changes on photoexcitation of Cu(I) phenanthroline metal-to-ligand charge transfer (MLCT) complexes by time-resolved diffraction
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Restricted photochemistry in the molecular solid state: Structural changes on photoexcitation of Cu(I) phenanthroline metal-to-ligand charge transfer (MLCT) complexes by time-resolved diffraction

机译：分子固态中受限制的光化学：通过时间分辨衍射对Cu（I）菲咯啉金属-配体电荷转移（MLCT）配合物进行光激发时的结构变化

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The excited-state structure of [Cu ~I[(1,10-phenanthroline-N, N′) bis(triphenylphosphine)] cations in their crystalline [BF _4] salt has been determined at both 180 and 90 K by single-pulse time-resolved synchrotron experiments with the modified polychromatic Laue method. The two independent molecules in the crystal show distortions on MLCT excitation that differ in magnitude and direction, a difference attributed to a pronounced difference in the molecular environment of the two complexes. As the excited states differ, the decay of the emission is biexponential with two strongly different lifetimes, the longer lifetime, assigned to the more restricted molecule, becoming more prevalent as the temperature increases. Standard deviations in the current Laue study are very much lower than those achieved in a previous monochromatic study of a Cu(I) 2,9-dimethylphenanthroline substituted complex (J. Am. Chem. Soc. 2009, 131, 6566), but the magnitudes of the shifts on excitation are similar, indicating that lattice restrictions dominate over the steric effect of the methyl substitution. Above all, the study illustrates emphatically that molecules in solids have physical properties different from those of isolated molecules and that their properties depend on the specific molecular environment. This conclusion is relevant for the understanding of the properties of molecular solid-state devices, which are increasingly used in current technology.
机译：已通过单脉冲在180 K和90 K下确定了它们的晶体[BF _4]盐中[Cu〜I [（1,10-菲咯啉-N，N'）双（三苯基膦）]阳离子的激发态结构。改进的多色Laue方法进行时间分辨同步加速器实验。晶体中的两个独立分子在MLCT激发时显示出畸变，其大小和方向不同，这归因于两种络合物的分子环境存在明显差异。由于激发态不同，发射的衰减是双指数的，具有两个截然不同的寿命，越长的寿命分配给受限制的分子，随着温度升高而变得越来越普遍。当前Laue研究中的标准偏差远低于先前对Cu（I）2,9-二甲基菲咯啉取代的络合物进行单色研究时获得的标准偏差（J. Am。Chem。Soc。2009，131，6566），但激发位移的幅度相似，表明晶格限制在甲基取代的空间效应上占主导地位。最重要的是，该研究着重说明了固体中的分子具有与分离的分子不同的物理特性，并且它们的特性取决于特定的分子环境。该结论与理解分子固态器件的特性有关，分子固态器件在当前技术中越来越多地使用。

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