Reticular Assembly of a Two‐Way Rod Metal‐Organic Framework through Orientation Control for Trace Benzene Capture

Comprehensive Summary

The advancement of reticular chemistry has significantly expanded the structural diversity of metal‐organic frameworks (MOFs). However, due to the inherent uncontrollability of rod secondary building units (SBUs) and the single parallel orientation of most rod SBUs, rod MOFs have limited structural diversity compared to MOFs with finite SBUs. In this work, we introduce an orientation‐controlled strategy for the rational design and synthesis of a two‐way rod MOF with novel pore structures. By employing a solvent modification approach, the linker torsion angles were adjusted, thereby reorienting the rod SBUs from one‐way parallelism in CPM‐74 to two‐way orthogonality, and affording a new rod MOF, CCNUF‐74. This material features smaller channel apertures and higher porosity than the one‐way CPM‐74, endowing it with a promising benzene vapor adsorption capacity (2.46 mmol·g ⁻¹ at 298 K) at P / P ₀ = 0.005. This work establishes orientation control as a robust methodology for the rational design of two‐way rod MOFs.