Ion-Directed Synthesis of Indium-Derived 2,5-Thiophenedicarboxylate Metal-Organic Frameworks: Tuning Framework Dimensionality

Abstract

Template directed synthesis of metal-organic frameworks (MOFs) is of increasing interest. Herein we report the synthesis of six new MOFs synthesized from 2,5-thiophenedicarboxylic acid (TDC) and InCl3. The new frameworks are formally two- (YCM-21) and one-dimensional (YCM-22) anionic, as well as three-dimensional neutral (YCM-23). YCM-22 contains an unprecedented dianionic [InCl3(κ2-O2CAr)2]2- node. The structural diversity represented by these materials is entirely controlled by addition of organic ammonium salts during the synthesis process. The role of the additives is briefly discussed with observed correlations of (1) hydrogen bonding and cation-π interactions influencing MOF dimensionality and (2) the presence of anionic chlorides creating a chlorine-rich metal center leading to a one-dimensional framework.