Towards Rational Modulation of In‐Plane Molecular Arrangements in Metal–Organic Framework Nanosheets

Abstract

Abstract A strategy to modulate the in‐plane structural arrangement in preferentially oriented crystalline metal–organic framework (MOF) nanosheets assembled by a two‐dimensional interfacial reaction between porphyrin units and metal ion linkers is reported. Starting with a tetratopic porphyrin MOF nanofilm, NAFS‐2, the framework size and shape are modified by employing specially designed building units, a trans ‐ditopic and an expanded tetratopic porphyrin, and Cu 2+ linkers. Reducing the number of binding parts affords a MOF nanosheet, NAFS‐31, with a distorted in‐plane structure. Extension of the peripheral substituents, while maintaining the tetratopic porphyrin geometry, results in marked unit cell size enlargement in an undistorted square grid in the MOF nanofilm, NAFS‐41. The exquisite geometric control that these structural modifications entail is valuable to allow switching of chemical/physical properties of the nanosheets and lead to realization of their use in nanotechnological applications.