Rouquet Etienne, Roy Chowdhury Madhusree, Garcia Gustavo A, Nahon Laurent, Dupont Jennifer, Lepère Valéria, Le Barbu-Debus Katia, Zehnacker Anne
Synchrotron SOLEIL, L'Orme des Merisiers, Départementale 128, F-91190, St Aubin, France.
Institut des Sciences Moléculaires d'Orsay (ISMO), CNRS, Université Paris-Saclay, F-91405, Orsay, France.
Nat Commun. 2023 Oct 9;14(1):6290. doi: 10.1038/s41467-023-42002-1.
An achiral chromophore can acquire a chiral spectroscopic signature when interacting with a chiral environment. This so-called induced chirality is documented in electronic or vibrational circular dichroism, which arises from the coupling between electric and magnetic transition dipoles. Here, we demonstrate that a chiroptical response is also induced within the electric dipole approximation by observing the asymmetric scattering of a photoelectron ejected from an achiral chromophore in interaction with a chiral host. In a phenol-methyloxirane complex, removing an electron from an achiral aromatic π orbital localised on the phenol moiety results in an intense and opposite photoelectron circular dichroism (PECD) for the two enantiomeric complexes with (R) and (S) methyloxirane, evidencing the long-range effect (~5 Å) of the scattering chiral potential. This induced chirality has important structural and analytical implications, discussed here in the context of growing interest in laser-based PECD, for in situ, real time enantiomer determination.
当一个非手性发色团与手性环境相互作用时，它可以获得手性光谱特征。这种所谓的诱导手性在电子或振动圆二色性中有所记载，其源于电偶极矩和磁偶极矩之间的耦合。在此，我们通过观察与手性主体相互作用的非手性发色团发射出的光电子的不对称散射，证明了在电偶极近似下也能诱导出手性光学响应。在苯酚 - 甲基环氧乙烷络合物中，从位于苯酚部分的非手性芳香π轨道移除一个电子，会导致与（R）和（S）甲基环氧乙烷形成的两种对映体络合物产生强烈且相反的光电子圆二色性（PECD），这证明了散射手性势的长程效应（约5 Å）。这种诱导手性具有重要的结构和分析意义，本文将在对基于激光的PECD（用于原位、实时对映体测定）兴趣日益浓厚的背景下进行讨论。
