Direct Construction of 2D Conductive Metal-Organic Frameworks from a Nonplanar Ligand: In Situ Scholl Reaction and Topological Modulation.

Two-dimensional conductive metal-organic frameworks (2D c-MOFs) are an emerging class of promising porous materials with high crystallinity, tunable structures, and diverse functions. However, the limited topologies and difficulties in synthesizing suitable organic linkers remain a great challenge for 2D c-MOFs synthesis and applications. Herein, two layered 2D c-MOF polymorphs with either a rhombus structure (sql-TBA-MOF) or kagome structure (kgm-TBA-MOF) were directly constructed via in situ Scholl reaction and coordination chemistry from a flexible and nonplanar tetraphenylbenzene-based ligand (8OH-TPB) in a one-pot manner. Interestingly, the kgm-TBA-MOF comprising hexagonal and triangular dual pores exhibit higher conductivities of 1.65 × 10-3 S/cm at 298 K and 3.33 × 10-2 S/cm at 353 K than that of sql-TBA-MOF (4.48 × 10-4 and 2.90 × 10-3 S/cm, respectively). Moreover, the morphology and topology can be modulated via the addition of ammonium hydroxide as modulator. The present work provides a new pathway for design, synthesis, and topological regulation of 2D c-MOFs.