Thermally stable porous supramolecular frameworks based on the metal and π–π stacking directed self‐assembly of 2,6‐pyridyldicarboxylic acid bis‐4‐pyridylamide

Abstract

AbstractWe report the formation of two thermally stable supramolecular structures based on 2,6‐pyridyldicarboxylic acid bis‐4‐pyridylamide (PyI) and bis(hexafluoroacetylacetonato)manganese(II) that exhibits a microporous structure with cavities bearing hydrogen bonding motifs that can enclathrate acetone and methanol molecules via well‐positioned hydrogen bonding interactions. Single‐crystal x‐ray diffraction in combination with thermogravimetric analysis and X‐ray powder diffraction (XRPD) studies were utilized to study the structure and thermal behavior of trans‐[Mn(hfacac)2(PyI)2]·2(CH3)2CO (1) and trans‐[Mn(hfacac)2(PyI)2]·2CH3OH (2). Our studies indicated that 1 and 2 are isostructural with respect to their supramolecular assembly and trap solvent molecules along the crystallographic b direction via the inwardly directed hydrogen bonding motifs of the PyI component. These solvent molecules can be thermally removed to generate a crystalline material with micropores bearing hydrogen bonding rich sites within an overall supramolecular matrix similar to 1 and 2. The removal of the guest solvent molecules is reversible and can be followed with XRPD. Copyright © 2003 John Wiley & Sons, Ltd.