We demonstrate the formation of highly symmetric crystalline hexagonal bipyramid-shaped superstructures in the self-assembly of dinuclear Pt(II) terpyridine complexes and show that it proceeds via a nonclassical crystallization (NCC) growth mechanism, which has not been reported in the supramolecular self-assembly of metal-organic complexes previously. Instead of identifying the classical hexagonal-shaped nuclei, we observed the intermediates of nanorods and pseudo-hexagonal shapes, establishing a previously unreported growth pattern of crystallization with direct experimental evidence for the NCC mechanism, which is the first of its kind in organic/organometallic supramolecular self-assembly. In addition, the crystal structures of the hexagonal bipyramids were found to be constructed from a weaving-like trimeric motif that elongates into a 2D hexagonal network by Pt···Pt, π-π, and hydrophobic interactions. It is envisaged that the current molecular packing strategy and the discovery of this NCC pathway will provide new insights into the rational design of geometric-shaped crystalline materials via supramolecular self-assembly.

我们证明了双核 Pt(II) 三联吡啶配合物自组装过程中高度对称结晶六方双锥体超结构的形成，并表明它是通过非经典结晶 (NCC) 生长机制进行的，这在超分子自组装中尚未报道-先前金属有机配合物的组装。我们没有识别经典的六边形核，而是观察了纳米棒和伪六边形形状的中间体，建立了以前未报道的结晶生长模式，并为 NCC 机制提供了直接的实验证据，这是有机/有机金属领域中的第一个。超分子自组装。此外，还发现六角双锥体的晶体结构是由类似编织的三聚基序构建的，该基序通过 Pt…Pt、π-π 和疏水相互作用伸长成二维六角形网络。预计当前的分子堆积策略和NCC途径的发现将为通过超分子自组装合理设计几何形状晶体材料提供新的见解。