Temperature-Dependent Supramolecular Isomerism of Lutetium-Aminoterephthalate Metal–Organic Frameworks: Synthesis, Crystallography, and Physical Properties

Abstract

Three supramolecular isomers of lutetium metal-organic framework, {Lu 2 (H 2 O) 4 (ATA) 3 ·4H 2 O} n (Lu-ATA@RT), {Lu 2 (H 2 O) 2 (C 3 H 7 NO) 2 (ATA) 3 } n (Lu-ATA@100) and{Lu 2 (C 3 H 7 NO)(ATA) 3 } n (Lu-ATA@150), have been obtained from the reaction of Lu(NO 3 ) 3 ·6H 2 O with 2-aminoterephthalic acid (ATA) at different temperatures. The resulting structures of Lu-ATA MOFs depend on the temperature applied during the synthesis, revealing a temperature-susceptible supramolecular isomerism. Single-crystal X-ray diffraction analyses suggest that new compounds with formula {Lu 2 (S) x (ATA) 3 } n (S = solvent: H 2 O, DMF) display different three-dimensional architectures which consist on dinuclear lutetium building units. The supramolecular isomer Lu-ATA@RT, formed at room temperature, has a pcu-net topology while its double interpenetrated analogue, Lu-ATA@100, assembles at 100 ºC under hydrothermal conditions. Hydrothermal synthesis at 150 ºC affords formation of the dense Lu-ATA@150 cage-like framework displaying a new hexagonal-packed net topology. All Lu-ATA isomeric phases are porous and display different gas-uptake behaviour towards carbon dioxide as a function of polymeric network arrangement. The luminescent properties of Lu-ATA frameworks in solid state as well as in suspension in the presence of different solvents reveal a solvent dependent emission.

Solvent-Dependent Formations of Supramolecular Isomers and a Single-Crystal to Single-Crystal Transformation from a Cyclic Dimer Complex to a One-Dimensional Coordination Polymer

“…Zaworotko has extended the concept of isomerism in monomeric metal complexes to oligomeric and polymeric coordination compounds and called it supramolecular isomerism. − Similar to the importance of polymorphism in the pharmaceutical area, , supramolecular isomerism is academically challenging and may serve the fundamental understanding for the development of metal-organic framework-based functional materials. − As controlling factors leading to supramolecular isomerism, temperature, − solvent, − template, − guest, , pH, − catenation, mole ratio, and concentration − have been known in the self-assembly of metallosupramolecules. However, the role of the solvent in this area has been less understood than other factors.…”

Temperature-Dependent Supramolecular Isomeric Zn(II)-Metal–Organic Frameworks and Their Guest Exchange

“…Supramolecular isomers which have an identical chemical composition but different network structures or morphologies have received increasing attention in the molecular and crystal engineering areas. − A number of studies on the supramolecular isomerism have been reported so far, and the factors such as temperature, − solvent, − template, − pH, , catenation, molar ratio, , and concentration − have been found to affect the formations of particular supramolecular isomers. However, it is still important to find and understand the factors that induce the formation of supramolecular isomers.…”

A novel three-dimensional tetranuclear CoII coordination polymer with water hexamers based on the V-shaped tetracarboxylate ligand 4-(2,4-dicarboxylatophenoxy)phthalate

“…CPs are typically built up through solvothermal or hydrothermal reactions in a closed autoclave, but it is still challenging to rationally design and construct CPs with desired topological structures due to complicated extrinsic factors, such as reaction temperature (Dikhtiarenko et al, 2016), template agents/additives (Hu et al, 2013), pH (Yang et al, 2012) and solvents (Xu et al, 2012). Since metal ions and organic ligands are the main inorganic and organic building units of CPs, it is generally believed that their selection and combination play a crucial role in determining the final network (Jiang et al, 2020).…”