Organic molecular assemblies that can conduct both electrons and protons are attractive materials, as they have important applications in organic electronics and fuel cells. Herein, two three-dimensional conducting framework organic salt (CFOS) single crystals with excellent electron and proton conductivity have been successfully synthesized by a simple drop-wise addition and crystallization method. The packing structure of CFOSs can be controlled through changing the central atom of building unit from a single carbon atom to a silicon atom, which in turn affects the electron and proton conductivity of CFOSs. Furthermore, the theoretical calculation results show that electron conduction occurs through the 3D super stacked π-conjugated network pathways whereas the proton conduction occurs via a novel combination of Grotthus and vehicular diffusion. The general design strategy and intuitive results in this work will provide practically useful insights in the preparation of new conducting framework organic salt single crystals with tuneable structures for specific applications.

可以传导电子和质子的有机分子组件是有吸引力的材料，因为它们在有机电子和燃料电池中具有重要应用。在此，通过简单的滴加结晶方法成功合成了两种具有优异电子和质子传导性的三维导电骨架有机盐（CFOS）单晶。CFOSs的堆积结构可以通过将结构单元的中心原子从单个碳原子改变为硅原子来控制，进而影响CFOSs的电子和质子电导率。此外，理论计算结果表明，电子传导通过 3D 超级堆叠 π 共轭网络路径发生，而质子传导通过Grotthus 和车辆扩散的新组合。这项工作的一般设计策略和直观结果将为制备具有可调谐结构的新型导电骨架有机盐单晶提供实用的见解，以用于特定应用。