Wang Ya-Jie, Shi Xiao-Yan, Xing Pengyao, Zang Shuang-Quan
Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou450001, People's Republic of China.
School of Chemistry and Chemical Engineering, Shandong University, Jinan250100, People's Republic of China.
JACS Au. 2023 Jan 20;3(2):565-574. doi: 10.1021/jacsau.2c00653. eCollection 2023 Feb 27.
Metallophilic interactions, which are ubiquitous among d metal complexes with linear coordination geometries, can direct one-dimensional assembly. However, the ability of these interactions to manipulate chirality at the hierarchical level largely remains unknown. In this work, we unveiled the role of Au···Cu metallophilic interactions in directing the chirality of multicomponent assemblies. -heterocyclic carbene-Au(I) complexes bearing amino acid residues formed chiral co-assemblies with [CuI] anions via Au···Cu interactions. These metallophilic interactions changed the molecular packing modes of the co-assembled nanoarchitectures from lamellar to columnar chiral packing. This transformation initiated the emergence, inversion, and evolution of supramolecular chirality, thereby affording helical superstructures, depending on the geometry of building units. In addition, the Au···Cu interactions altered the luminescence properties and induced the emergence and amplification of circularly polarized luminescence. This work, for the first time, revealed the role of Au···Cu metallophilic interactions in modulating supramolecular chirality, paving the way for the construction of functional chiroptical materials based on d metal complexes.
亲金属相互作用在具有线性配位几何结构的d金属配合物中普遍存在,能够引导一维组装。然而,这些相互作用在层次水平上操纵手性的能力在很大程度上仍然未知。在这项工作中,我们揭示了金···铜亲金属相互作用在引导多组分组装体手性方面的作用。带有氨基酸残基的杂环卡宾-金(I)配合物通过金···铜相互作用与[CuI]阴离子形成手性共组装体。这些亲金属相互作用将共组装纳米结构的分子堆积模式从层状转变为柱状手性堆积。这种转变引发了超分子手性的出现、反转和演变,从而根据构建单元的几何形状提供螺旋超结构。此外,金···铜相互作用改变了发光性质,并诱导了圆偏振发光的出现和放大。这项工作首次揭示了金···铜亲金属相互作用在调节超分子手性方面的作用,为基于d金属配合物的功能性手性光学材料的构建铺平了道路。