Herein, we report on the guest-responsive hierarchical self-assembly of dissymmetric cage DC-1 with an intrinsic dipole along its C₃-symmetric axis. DC-1 molecules self-assemble into supramolecular columns with the molecular dipoles aligned along the columnar axis. Mediated by different host–guest interactions of ethyl acetate (EtOAc) and chloroform (CHCl₃), the columns are arranged in an antiparallel and parallel fashion, respectively, leading to a switch of the centrosymmetric and noncentrosymmetric superstructures. The symmetry of the molecular packing of DC-1 molecules of the noncentrosymmetric crystalline phase is therefore broken, producing a supramolecular ferroelectric with second-harmonic generation and piezoelectric responses. We demonstrate that cages can serve as promising building blocks for the discovery of supramolecular materials with emergent functions and properties, including but not limited to, organic ferroelectrics and nonlinear optics.

在这里，我们报告了不对称笼子的来宾响应分层自组装 DC-1具有沿其C ₃对称轴的固有偶极子。 DC-1分子自组装成超分子柱，分子偶极子沿柱轴排列。在乙酸乙酯 (EtOAc) 和氯仿 (CHCl ₃ )的不同主客体相互作用的介导下，柱子分别以反平行和平行方式排列，导致中心对称和非中心对称超结构的转换。分子堆积的对称性 DC-1因此，非中心对称晶相的分子被破坏，产生具有二次谐波和压电响应的超分子铁电体。我们证明了笼子可以作为发现具有新兴功能和特性的超分子材料的有前途的基石，包括但不限于有机铁电体和非线性光学。