Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France.
Chemistry. 2010 May 25;16(20):5976-6005. doi: 10.1002/chem.200903234.
Aza[n]helicene phosphole derivatives have been prepared from aza[n]helicene diynes by the Fagan-Nugent route. Their photophysical properties (UV/Vis absorption and emission behavior) have been evaluated. Their behavior as P,N chelates towards coordination to Pd(II) and Cu(I) has been investigated: metal-bis(aza[n]helicene phosphole) assemblies are formed by a highly stereoselective coordination process, as demonstrated by X-ray crystallography. An aza[6]helicene phosphole bearing an enantiopure helicene part has been obtained, which allows the preparation of enantiopure Pd(II) and Cu(I) complexes with original topologies and high molar rotation (MR) and circular dichroism (CD). The structure-property relationship established from the experimental data has been studied in detail by theoretical studies (TDDFT calculations of UV/Vis, CD, and MR). Aza[n]helicene phosphole derivatives show pi conjugation extended over the entire molecule, and its influence on the MR of aza[6]helicene phosphole 5 c has been demonstrated. Finally, it has been shown that the nature of the metal (coordination geometry and electronic interaction) can have a great impact on the amplitude of the chiroptical properties in metal-bis(aza[n]helicene phosphole) assemblies.
氮杂[ n ]轮烯膦咯衍生物已通过 Fagan-Nugent 路线由氮杂[ n ]轮烯二炔制备。评估了它们的光物理性质（UV / Vis 吸收和发射行为）。研究了它们作为 P ， N 螯合剂与 Pd （ II ）和 Cu （ I ）配位的行为：通过 X 射线晶体学证明，金属双（氮杂[ n ]轮烯膦咯）组装物通过高度立体选择性配位过程形成。获得了带有手性纯螺旋部分的氮杂[ 6 ]轮烯膦咯，这允许制备具有原始拓扑结构和高摩尔旋转（MR ）和圆二色性（CD ）的手性纯 Pd （ II ）和 Cu （ I ）配合物。通过理论研究（UV / Vis ， CD 和 MR 的 TDDFT 计算）详细研究了从实验数据得出的结构 - 性质关系。氮杂[ n ]轮烯膦咯衍生物显示出整个分子上的π共轭延伸，并且已经证明了其对氮杂[ 6 ]轮烯膦咯 5 c 的 MR 的影响。最后，表明金属的性质（配位几何形状和电子相互作用）可以对金属双（氮杂[ n ]轮烯膦咯）组装物中的手性光学性质的幅度产生重大影响。
