Porous Lanthanide–Organic Frameworks: Control over Interpenetration, Gas Adsorption, and Catalyst Properties

Abstract

Two isomorphous lanthanide−organic frameworks, Ln(BDC) 1.5 (DMF)-(H 2 O) (Ln = Er (1), Tm (2)) have been synthesized based on 1,4-benzenedicarboxylic acid (H 2 BDC). Because of the 2-fold interpenetration, the pores are partly blocked and there are no significant gas adsorptions for these two interpenetrating nets. Through control over interpenetration by applying an organic ligand with hindrance groups or replacing coordinated solvent molecules with a chelating ligand, three noninterpenetrating lanthanide−organic frameworks, Er 2 (BDC) 3 (phen 5), possessing the same topology with 1 and 2, have been synthesized and characterized. Further changing reaction conditions, three other porous lanthanide−organic frameworks with different structures with 1−5, 7), and Sm(TBDC) 1.5 (phen)-(H 2 O)•DMF•H 2 O (8), have been constructed. Gas sorption measurements for 5, 6, 7, and 8 have been carried out and revealed that these materials possess permanent porosity. The catalytic property for complex 6 has also been studied.

Controlling dimensionality via a dual ligand strategy in Ln-thiophene-2,5-dicarboxylic acid-terpyridine coordination polymers

“…1, 2 As such, these materials have proven particularly attractive for applications including luminescence, [3][4][5] sensing (cation, anion or molecular), 6-8 gas storage, [9][10][11] heterogeneous catalysis, [12][13][14][15] and magnetism. Crystalline hybrid materials are an area of structural chemistry that include coordination polymers (CPs) and metal-organic frameworks (MOFs), which can both be defined as assemblies of Ln 3+ metal centers polymerized through organic linkers resulting in diverse topologies of higher dimensionality.…”

Lanthanide contraction effects on the structures, thermostabilities, and CO2 adsorption and separation behaviors of isostructural lanthanide–organic frameworks

“…34,[48][49][50] These LOFs consist of BTC ligands coordinated to lanthanide ions in a 1 : 1 stoichiometric ratio. 34,[48][49][50] These LOFs consist of BTC ligands coordinated to lanthanide ions in a 1 : 1 stoichiometric ratio.…”

“…Various functionalization methods are available to introduce different metal centers to MOFs to improve their thermostability. Although considerable investigation has been carried out on the gas adsorption properties of LOFs, 31,39,41,[46][47][48][49][50][51][52][53] it is also necessary to prepare LOFs on a large scale for their potential industrial applications. [32][33][34][35][36][37][38] Recently, several lanthanide benzenetricarboxylates (LnBTCs) have been investigated as promising candidates for gas storage and separation.…”

Extending the lanthanide–terephthalate system: Isolation of an unprecedented Tb(III)-based coordination polymer with high potential porosity and luminescence properties

“…This rode-like non-toxic ligand has led to numerous archetypical transition metal-based coordination polymers [3][4][5][6]. Since the pioneer work of Reineke et al [7,8], this ligand also allows to elaborate lanthanide-based compounds [9][10][11][12][13][14][15][16][17][18] with interesting potential porosity [8,[19][20][21][22][23][24][25][26] and/or luminescent [7,[27][28][29][30][31][32][33] properties (Table 1). On the other hand our group is involved for several years in the synthesis of octahedral hexanuclear lanthanide-based complex and their use as molecular Table 1 Reported structural properties of lanthanide-based coordination polymers involving bdc [2-7-33,36].…”