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.

Crystal structure of catena-poly[(μ2-3-(1H-pyrazol-4-yl)-5-(pyridin-4-yl)-1,2,4-triazole-κ N:N′)-bis(benzoato-κO)zinc(II)], C24H18N6O4Zn

“…In that regard, the N-donor ligands and aromatic carboxylic acid are perhaps the most promising candidates, because they can interact with a metal surface by both π electrons and the lone-pair electrons at the nitrogen atom and oxygen atom. Hence, they provide access to diverse coordination polymer topologies [9][10][11][12]. In light of the interesting structural diversity in previously reported zinc(II) Metal-Organic frameworks based on triazole-carboxylate [13,14], we set about attempts to prepare transition metal coordination polymers containing the eas- [15].…”

N-donor co-ligands driven two new Co(II)- coordination polymers with bi- and trinuclear units: Crystal structures, and magnetic properties

“…Mn(II), have received increasing attention, owing to its high spin ground state can be obtained from strong exchange interactions between 3d electrons [1][2][3][4][5][6][7][8][9][10]. Noted that, the development of coordination chemistry, many research efforts have been devoted to novel ways to fabricate, characterize and explore fundamental magnetic phenomena [11][12][13][14][15][16][17][18][19][20][21][22][23]. Coordination polymers (CPs) with polynuclear units based on Co(II) and Mn(II) have fascinating architectures and physical properties with widespread applications, such as catalysis, sorption, magnetism and electrical conductivity [24][25][26][27][28][29][30].…”

Gas Sorption Properties of a New Three-Dimensional In-ABDC MOF With a Diamond Net

“…The most common counter-cations are either Me 2 NH + 2 or Et 2 NH + 2 which can be in-situ generated from the solvents: N,Ndimethylformamide (DMF) or N,N-diethylformamide (DEF). A range of ammonium-based cations can also be added into the reaction mixture to facilitate the formation of anionic In-MOFs (Chen et al, 2009;Lin et al, 2012;Huang et al, 2014;Mihaly et al, 2016;Zhao et al, 2018). In these cases, the counter-cations found in MOFs are the added ammonium-based cations.…”