Metal–organic frameworks (MOFs) with tunable structures and unique host–guest chemistry have emerged as promising candidates for conductive materials. However, the tunability of conductivity and porosity in conductive MOFs, as well as their interrelationship, still lacks a systematic study. Herein, we report the synthesis of a series of 3D copper MOFs (NU-4000 to NU-4003) using a triphenylene-based hexatopic carboxylate linker. By modulating the ratio of mixed solvents, distinct structural topologies and π–π stacking arrangements were achieved, resulting in electrical conductivities ranging from insulators (<10^–6 S/cm) to semiconductors (10^–8∼10² S/cm). Among them, NU-4003 features continuous π–π stacking and exhibits a conductivity of 1.7 × 10^–6 S/cm. To further enhance the conductivity, we encapsulated C₆₀, a strong electron acceptor, within the circular channels of NU-4003, resulting in a remarkable conductivity increase to 140 S/cm with approximately 100% pore occupancy. Even at lower C₆₀ loadings that leave 54% of the pore volume accessible, the conductivity remains exceptionally high at 104 S/cm. This represents an eight-order magnitude enhancement and positions NU-4003-C₆₀ as one of the most conductive 3D MOFs reported to date. This work integrates two charge transport pathways (through-space and electron donor-acceptor interactions) into a single MOF host–guest material, achieving a significant enhancement in conductivity. This study demonstrates the potential of combining host–guest chemistry and π–π stacking to design conductive MOFs with permanent porosity maintained, providing a blueprint for the development of next-generation materials for electronic and energy-related applications.

中文翻译：

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π 堆叠 3D 金属有机框架的溶剂导向组装，通过 C60 封装增强可调导电性

具有可调结构和独特主客体化学性质的金属有机框架 （MOF） 已成为导电材料的有前途的候选材料。然而，导电 MOF 中电导率和孔隙率的可调性以及它们之间的相互关系仍然缺乏系统的研究。在本文中，我们报道了使用三苯基六位羧酸酯接头合成一系列 3D 铜 MOF （NU-4000 至 NU-4003）。通过调节混合溶剂的比例，实现了不同的结构拓扑和 π-π 堆叠排列，从而产生从绝缘体 （<10^–6 S/cm） 到半导体 （10^–8∼10² S/cm） 的电导率。其中，NU-4003 具有连续π-π堆叠的特点，电导率为 1.7 × ^10-6 S/cm。为了进一步提高电导率，我们在 NU-4003 的圆形通道内封装了强电子受体 C₆₀，从而将电导率显着提高到 140 S/cm，孔隙占用率约为 100%。即使在较低的 C₆₀ 负载量下，仍可接近 54% 的孔隙体积，电导率仍保持在 104 S/cm 的极高水平。这代表了 8 个数量级的增强，并使 NU-4003-C₆₀ 成为迄今为止报道的导电性最强的 3D MOF 之一。这项工作将两种电荷传输途径（通过空间和电子供体-受体相互作用）集成到单个 MOF 主客体材料中，实现了电导率的显着增强。这项研究展示了将主客体化学和 π-π 堆叠相结合以设计保持永久孔隙率的导电 MOF 的潜力，为开发用于电子和能源相关应用的下一代材料提供了蓝图。