Electrically conducting 2D metal–organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van der Waals stacked materials. However, understanding their intrinsic properties remains a challenge because their crystals are too small or of too poor quality for crystal structure determination. Here, we report atomically precise structures of a family of 2D π-conjugated MOFs derived from large single crystals of sizes up to 200 μm, allowing atomic-resolution analysis by a battery of high-resolution diffraction techniques. A designed ligand core rebalances the in-plane and out-of-plane interactions that define anisotropic crystal growth. We report two crystal structure types exhibiting analogous 2D honeycomb-like sheets but distinct packing modes and pore contents. Single-crystal electrical transport measurements distinctively demonstrate anisotropic transport normal and parallel to the π-conjugated sheets, revealing a clear correlation between absolute conductivity and the nature of the metal cation and 2D sheet packing motif.

导电的2D金属有机框架（MOF）引起了人们的极大兴趣，因为它们的6D六角形网格模仿了石墨和其他2D范德华堆叠材料。但是，了解其固有性质仍然是一个挑战，因为它们的晶体太小或质量太差，无法确定晶体结构。在这里，我们提出一个家庭2D的原子精确结构π衍生自最大尺寸为200μm的大型单晶的共轭MOF，可通过一系列高分辨率衍射技术进行原子分辨率分析。设计的配体核可重新平衡定义各向异性晶体生长的面内和面外相互作用。我们报告了两种晶体结构类型，它们表现出相似的二维蜂窝状片材，但具有不同的堆积模式和孔含量。单晶电输运测量结果清楚地表明了各向异性的输运，其垂直且平行于π共轭薄片，揭示了绝对电导率与金属阳离子和2D薄片堆积图案的性质之间的明显关联。