Wang Ya-Jie, Shi Xiao-Yan, Xing Pengyao, Dong Xi-Yan, Zang Shuang-Quan
Henan Key Laboratory of Crystalline Molecular Functional Materials, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, People's Republic of China.
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China.
Sci Adv. 2023 Nov 24;9(47):eadj9013. doi: 10.1126/sciadv.adj9013. Epub 2023 Nov 22.
Understanding the fundamentals and applications of chirality relies substantially on the amplification of chirality through hierarchical assemblies involving various weak interactions. However, a notable challenge remains for metal clusters chiral assembly driven by halogen bonding, despite their promising applications in lighting, catalysis, and biomedicine. Here, we used halogen bonding-driven assembly to achieve a hierarchical degree of achiral emissive clusters. From single crystals to one-dimensional ribbons and then to helixes, the morphologies were primarily modulated by intermolecular halogen bonding that evoked by achiral or/and chiral iodofluorobenzene (IFBs) molecules. Concomitantly, the luminescence and circularly polarized luminescence (CPL) changed a lot, ultimately leading to a substantial increase in the luminescence dissymmetry -factor () of 0.036 in the supramolecular helix. This work opens an avenue for hierarchical assemblies using predesigned metal clusters as building blocks though directional halogen bonding. This achievement marks a noteworthy advancement in the field of nanosized inorganic functional blocks.
理解手性的基本原理和应用在很大程度上依赖于通过涉及各种弱相互作用的分级组装来放大手性。然而，尽管金属簇在手性组装在照明、催化和生物医学等领域有着广阔的应用前景，但由卤键驱动的金属簇手性组装仍然面临着一个显著的挑战。在这里，我们利用卤键驱动的组装实现了非手性发光簇的分级程度。从单晶到一维带状物，再到螺旋结构，其形态主要由非手性或/和手性碘氟苯（IFB）分子引发的分子间卤键调节。与此同时，发光和圆偏振发光（CPL）发生了很大变化，最终导致超分子螺旋结构的发光不对称因子（）大幅增加至0.036。这项工作为利用预先设计的金属簇作为构建块通过定向卤键进行分级组装开辟了一条途径。这一成果标志着纳米级无机功能块领域的一项值得注意的进展。
