Magnetic, luminescence, topological and theoretical studies of structurally diverse supramolecular lanthanide coordination polymers with flexible glutaric acid as a linker

Kumar, Manesh; Qiu, Cheng-Qiang; Zarȩba, Jan K.; Frontera, Antonio; Jassal, Amanpreet Kaur; Sahoo, Subash Chandra; Liu, Sui‐Jun; Sheikh, Haq Nawaz

doi:10.1039/c9nj03664d

Cited by 31 publications

(21 citation statements)

References 113 publications

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“…Considering that the −ΔS m value is inversely proportional to the molecular weight under the same conditions, it is highly necessary to design and synthesize magnetorefrigerant materials with a small molecular weight. [63][64][65][66] Oxalic acid and malonic acid, as important chemical raw materials, are widely used to assemble Gd(III)-based magnetic refrigeration materials due to their small molecular weight. In 2019, using Gd 2 O 3 , propandioic acid (H 2 pda) and oxalic acid (H 2 ox) as starting materials, a new 2D Gd(III)-based MOF with the formula [Gd(pda)(ox) 0.5 (H 2 O) 2 ] n (28) was prepared by our group.…”

Section: Dicarboxylate Ligandsmentioning

confidence: 99%

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Gd(iii)-Based inorganic polymers, metal–organic frameworks and coordination polymers for magnetic refrigeration

Xiang

Shen

et al. 2022

CrystEngComm

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Section: Dicarboxylate Ligandsmentioning

confidence: 99%

Section: Gd(iii)-based Mofs and Cps Derived From Carboxylate Ligands ...mentioning

confidence: 99%

Gd(iii)-Based inorganic polymers, metal–organic frameworks and coordination polymers for magnetic refrigeration

Xiang

Shen

et al. 2022

CrystEngComm

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“…The use of ditopic aliphatic ligands in the synthesis of CPs is limited by the stability of the conformer, the size of the ligand and the architecture of the polymer. Additionally, it is important to note the high number of reports with short dicarboxylates (carbon numbers between 2 and 5, Figure 1) forming Ln-CPs or An-CPs (Ln = lanthanides and An = actinides) [27][28][29][30]. The oxalate anion is not a flexible ligand and contributes with rigidity and stability in the resulting CP.…”

Section: Coordination Polymers Based On Oxalate Linkermentioning

confidence: 99%

“…Similarly, the glutarate presents a wide range of C-C-C-O torsion angles as well as different configurations around the methylene scaffold [88][89][90]. According to Kumar et al [30], it is interesting to differentiate between two types of compounds: (i) those without ancillary co-ligands and (ii) those with ancillary co-ligand [30]. Further, there is one report of complexes formed with H 2 HFG ligand [91], with Eu 3+ and Tb 3+ ions giving rise to dimeric assemblies with the formula [Ln 2 (HFG) 2 (phen)4(H 2 O) 6 ].…”

Section: Sm-hexafluoroglutarato Cpsmentioning

confidence: 99%

Highlighting Recent Crystalline Engineering Aspects of Luminescent Coordination Polymers Based on F-Elements and Ditopic Aliphatic Ligands

2022

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Three principal factors may influence the final structure of coordination polymers (CPs): (i) the nature of the ligand, (ii) the type and coordination number of the metal center, and (iii) the reaction conditions. Further, flexible carboxylate aliphatic ligands have been widely employed as building blocks for designing and synthesizing CPs, resulting in a diverse array of materials with exciting architectures, porosities, dimensionalities, and topologies as well as an increasing number of properties and applications. These ligands show different structural features, such as torsion angles, carbon backbone number, and coordination modes, which affect the desired products and so enable the generation of polymorphs or crystalline phases. Additionally, due to their large coordination numbers, using 4f and 5f metals as coordination centers combined with aliphatic ligands increases the possibility of obtaining different crystal phases. Additionally, by varying the synthetic conditions, we may control the production of a specific solid phase by understanding the thermodynamic and kinetic factors that influence the self-assembly process. This revision highlights the relationship between the structural variety of CPs based on flexible carboxylate aliphatic ligands and f-elements (lanthanide and actinides) and their outstanding luminescent properties such as solid-state emissions, sensing, and photocatalysis. In this sense, we present a structural analysis of the CPs reported with the oxalate ligand, as the one rigid ligand of the family, and other flexible dicarboxylate linkers with –CH2– spacers. Additionally, the nature of the luminescence properties of the 4f or 5f-CPs is analyzed, and finally, we present a novel set of CPs using a glutarate-derived ligand and samarium, with the formula [2,2′-bipyH][Sm(HFG)2 (2,2′-bipy) (H2O)2]•(2,2′-bipy) (α-Sm) and [2,2′-bipyH][Sm(HFG)2 (2,2′-bipy) (H2O)2] (β-Sm).

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“…21,22 Hence, the utilization of flexible linkers has proven to be one of the successful strategies to explore the structural diversity of LnCPs. 23 In addition, the solvent also plays a vital role in the self-assembly process of coordination polymers directly by coordinating with the metal center or indirectly templating the crystal growth process. 24,25 When solvents are directly involved in the coordination assembly by coordinating with the metal centers depending upon the bulkiness and steric hindrance of the solvent, it influences the symmetry of the metal coordination sphere thereby affecting the self-assembly process.…”

Section: ■ Introductionmentioning

confidence: 99%

Solvent Influence in Obtaining Diverse Coordination Symmetries of Dy(III) Metal Centers in Coordination Polymers: Synthesis, Characterization, and Luminescent Properties

Phukan

Goswami

Lipstman

et al. 2020

Crystal Growth & Design

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Six new Dy(III)-containing coordination polymers (CPs) have been synthesized emphasizing the role of solvent molecules in directing the formation of the Dy(III) coordination sphere which in turn influences the dimensionality of the coordination polymer, thermal stability, and emission properties. An isophthalate-based flexible ligand 5-[(anthracen-9-ylmethyl)amino]-isophthalic acid (H 2 L) with different solvents such as dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), diethylformamide (DEF), and N-donor linkers phen (1,10-phenanothroline) and pyridine (py) was employed to o b t a i n s i x d i ff e r e n t c o o r d i n a t i o n p o l y m e r s , 5), and [Dy(L)(NO 3 )(py) 2 •py] n (6), respectively. All the compounds were characterized by IR spectroscopy and thermogravimetric analysis, and unambiguously characterized by single crystal X-ray crystallography. The bulky anthracenyl group of the linker H 2 L in combination with the solvent molecules significantly alters the coordination symmetry of the Dy(III) coordination sphere in the polymers in the manner: D 2d in 1, C 2v and D 4d in 2, C 4v and C s in 3, C 5v in 4, D 4d in 5, and D 2d in 6. The coordination symmetry plays an interesting role in sensitization of lanthanide emission. The emission maxima of compounds 1−6 vary from the blue region to the yellow region significantly due to coordination symmetry expressed by the Dy(III) centers, which in turn depends upon the coordinated solvent molecule. The thermogravimetric profile indicates the thermal stability of the solvent free compounds up to 300 °C.

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Magnetic, luminescence, topological and theoretical studies of structurally diverse supramolecular lanthanide coordination polymers with flexible glutaric acid as a linker

Abstract: This contribution explores the topological, supramolecular, magnetic and luminescent properties of previously unknown CPs, which fall into category of glutarates without auxiliary coligands.

Cited by 31 publications

References 113 publications

Gd(iii)-Based inorganic polymers, metal–organic frameworks and coordination polymers for magnetic refrigeration

Gd(iii)-Based inorganic polymers, metal–organic frameworks and coordination polymers for magnetic refrigeration

Highlighting Recent Crystalline Engineering Aspects of Luminescent Coordination Polymers Based on F-Elements and Ditopic Aliphatic Ligands

Solvent Influence in Obtaining Diverse Coordination Symmetries of Dy(III) Metal Centers in Coordination Polymers: Synthesis, Characterization, and Luminescent Properties

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