Graduate School of Pure and Applied Sciences and Tsukuba Research Center for Interdisciplinary Materials Science (TIMS), University of Tsukuba , 1-1-1, Tennodai, Tsukuba, Ibaraki 305-8571, Japan.
J Am Chem Soc. 2014 Oct 8;136(40):14299-306. doi: 10.1021/ja507913u. Epub 2014 Sep 24.
A C3-symmetric chiral concave molecule having a phosphorus atom at the center was synthesized, and its enantiomers were resolved. The chiral concave shape and absolute structure of the concave molecules were revealed by X-ray analysis. The concave molecule exhibited intense chiroptical properties with a large anisotropy, which was derived from molecular orbitals delocalized to the side chains. In the co-crystal with pristine C60, four of the enantiopure concave molecules perfectly wrapped the surface of C60. MALDI-TOF mass, NMR, and circular dichromism spectra also supported the concave/convex interaction between the concave molecule and fullerene. These results suggest that the phosphorus-containing molecule with a concave shape plays an important role as a chiral host molecule for C60.
一种具有中心磷原子的 C3 对称手性凹型分子被合成，并对其对映异构体进行了拆分。通过 X 射线分析揭示了凹型分子的手性凹型形状和绝对结构。凹型分子表现出强烈的手性光学性质，具有较大的各向异性，这是源于分子轨道离域到侧链。在与原始 C60 的共晶中，四个对映纯凹型分子完美地包裹了 C60 的表面。MALDI-TOF 质量、NMR 和圆二色光谱也支持凹型分子和富勒烯之间的凹凸相互作用。这些结果表明，具有凹型形状的含磷分子在作为 C60 的手性主体分子方面发挥着重要作用。
