Coordination polymers of lanthanide complexes with benzene dicarboxylato ligands

Luo, Yu‐Hui; Yue, Fengxia; Yu, Xiaofeng; Chen, Xin; Zhang, Hong

doi:10.1039/c3ce40357b

Cited by 25 publications

(5 citation statements)

References 41 publications

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“…Lanthanide-based coordination polymers attract great interest. − Indeed, because of the unique optical , and magnetic properties of the lanthanide ions, they present great interest in various technological fields such as molecular thermometry, − chemical sensing, − light and display, , or the fight against counterfeiting, − for instance. Therefore, the quest for highly luminescent lanthanide-based coordination polymers is a continuous concern. ,− Because lanthanide ions present no structuring effect, most of the reported studies focus their attention on the choice of the ligand. ,,− This synthetic strategy offered very luminescent coordination polymers with high quantum yields. − Some recent works suggest that an extended inorganic sublattice surrounded by ligands that act both as antennas and as spacers is relevant as far as highly luminescent coordination polymers are targeted. − …”

Section: Introductionmentioning

confidence: 99%

Hexanuclear Molecular Precursors as Tools to Design Luminescent Coordination Polymers with Lanthanide Segregation

et al. 2021

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Solvothermal reactions between hexanuclear complexes with the general chemical formula [Ln 6 (μ 6 -O)(μ 3 -OH) 8 (NO 3 ) 6 (H 2 O) 12 ]•2NO 3 •2H 2 O and 2-bromobenzoic acid (2-bbH) lead to a series of isostructural one-dimensional coordination polymers with the general chemical formula [Ln 2 (2-bb) 6 ] ∞ with Ln = Sm, Eu, Tb, Dy, and Y. These coordination polymers crystallize in the orthorhombic space group Fdd2 (No. 43) with the following cell parameters: a = 29.810(3) Å, b = 51.185(6) Å, c = 11.7913( 14) Å, V = 17992(4) Å 3 , and Z = 16. The europium-and terbium-based derivatives show sizable luminescence intensities under UV excitation. Isostructural heterolanthanide coordination polymers have also been prepared. Their luminescent properties suggest that during the synthetic process the starting hexanuclear complexes are destroyed but strongly influence the distribution of the different lanthanide ions over the metallic sites of the crystal structure. Indeed, it is possible to prepare heterolanthanide coordination polymers in which lanthanide-ion segregation is controlled.

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Section: Introductionmentioning

confidence: 99%

Hexanuclear Molecular Precursors as Tools to Design Luminescent Coordination Polymers with Lanthanide Segregation

et al. 2021

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“…Terbium-based Ln-CP 8 shows four emission peaks at 488, 542, 593, and 623 nm, all of which can be attributed to radiative relaxation from the 5 D 4 excited state of Tb 3+ tothe 7 F J state ( J = 6, 5, 4, 3, respectively). − The 5 D 4 → 7 F 5 transition at 542 nm has the highest intensity and contributes the most to the intense green emission in Ln-CP 8 . Excitation spectra of 6 and 8 reveal typical sets of excitation bands for the Eu 3+ and Tb 3+ ions, and assignments of the bands are provided in Figure .…”

Section: Results and Discussionmentioning

confidence: 99%

Lanthanide Contraction in Action: Structural Variations in 13 Lanthanide(III) Thiophene-2,5-dicarboxylate Coordination Polymers (Ln = La–Lu, Except Pm and Tm) Featuring Magnetocaloric Effect, Slow Magnetic Relaxation, and Luminescence-Lifetime-based Thermometry

Kumar

Zarȩba

et al. 2020

Crystal Growth & Design

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Thirteen new three-dimensional lanthanide(III)-2,5-thiophenedicarboxylate coordination polymers (Ln-CPs) with general formulas of [Ln2(2,5-TDA)3(DMA)2(H2O)] n (Ln-CPs 1–4) and [Ln2(2,5-TDA)3(DMA)2] n (Ln-CPs 5–13) (where 2,5-TDA2– = 2,5-thiophedicarboxylate dianion, DMA = N,N′-dimethylacetamide, and Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Yb (12) Lu (13)) have been synthesized solvothermally under two different temperature conditions in a DMA–H2O mixed solvent system. A structural analysis discloses that the four Ln-CPs 1–4 crystallize in the orthorhombic space group Pna21, whereas the eight Ln-CPs 5–8 and 10–13 crystallize in the triclinic P̅1 space group and Ln-CP 9 (Dy) adopts the monoclinic P2/c space group. The distinct crystal structures and coordination features indicate that lanthanide contraction, ancillary DMA molecules, and different coordination modes identified for 2,5-TDA2– play deciding roles in the self-assembly of Ln-CPs 1–13. The Ln(III) centers in compounds 1–13 exhibit three different coordination numbers, 9 (only 1; around La1), 8 (1–8 and 10–12), and 7 (4, 8, 9 and 11–13) with monocapped-square-antiprismatic, bicapped-trigonal-prismatic, and monocapped-trigonal-prismatic geometries, respectively. The title compounds display distinct 3D coordination frameworks with dinuclear (La2O15; for 1 and Ln2O14; for 2–4) SBUs and tetranuclear [Ln4O28] SBUs (for compounds 5–13). Variable-temperature magnetic susceptibility measurements were investigated for Ln-CPs 7–11 with an applied dc field of 1 kOe. The weak antiferromagnetic interaction and small ligand/metal mass ratio make Ln-CP 7 (Gd) a good candidate for low-temperature magnetic refrigeration with an impressive −ΔS m max = 31.0 J kg–1 K–1 (63.6 mJ cm–3 K–1) at T = 2 K and ΔH = 7 T. Furthermore, the frequency and temperature dependences of the alternating current (ac) susceptibilities have been studied to explore the magnetic dynamics of Ln-CPs 8–10. Importantly, for compound 9 (Dy), the χ′m and χ″m curves and Cole–Cole plots at 2–6 K suggest the existence of slow magnetic relaxation behavior. Luminescence thermometry studies have been performed at 298–373 K for Ln-CPs 6 and 8. The Eu analogue (6) features a weak temperature dependence of luminescence lifetime (relative sensitivities of 0.43% K–1 and 0.34% K–1 at 298 and 373 K, respectively), whereas the Tb analogue (8) is a good lifetime-based luminescent thermometer with a constant relative sensitivity value of 1.35% K–1 in the investigated temperature range.

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“…The excitation spectrum of 3 (Figure ) shows the sharp peaks at 286, 298, 304, 318, 327, 362, 366, 375, 381, 394, 416, 464, 527, and 536 nm, corresponding to the 7 F 0 → 5 H 6 , 5 I 7 / 7 F 1 → 5 I 7 , 7 F 0 → 5 F 4 / 7 F 1 → 5 I 4 , 7 F 0 → 5 F 2 / 7 F 1 → 5 F 1 , 7 F 0 → 5 H 6 , 7 F 1 → 5 H 7 , 7 F 0 → 5 D 4 , 7 F 1 → 5 D 4 , 7 F 0 → 5 G 6 , 7 F 1 → 5 G 3 / 5 G 5 / 5 G 6 , 7 F 1 → 5 L 6 , 7 F 1 → 5 D 3 , 7 F 1 → 5 D 2 , and 7 F 0 → 5 D 1 transitions of Eu III , respectively. [23b] The emission spectrum of 3 (Figure ) under 395 nm excitation exhibits a series of characteristic emissions of Eu III at 579 ( 5 D 0 → 7 F 0 ), 593 ( 5 D 0 → 7 F 1 ), 615 ( 5 D 0 → 7 F 2 ), 650 ( 5 D 0 → 7 F 3 ), and 690 nm ( 5 D 0 → 7 F 4 ), respectively . Among these emission peaks, the 5 D 0 → 7 F 2 transition is most striking, indicating the intense red luminescence of 3 .…”

Section: Resultsmentioning

confidence: 99%

Two Series of Substituent‐Group‐Directed Adipate‐Based Lanthanide Coordination Polymers: Syntheses, Structures, Photoluminescence, and Magnetism

Zhang

Liu

et al. 2020

Eur J Inorg Chem

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Two series of lanthanide‐organic coordination polymers (CPs) [Ln2(L1)3(H2O)4] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), and Dy (6), H2L1 = 3‐methyl‐adipic acid] and [Ln4(L2)6(H2O)4] [Ln = Nd (7), Sm (8), Eu (9), Gd (10), Tb (11), and Dy (12), H2L2 = 3‐tert‐butyl‐adipic acid] have been synthesized by the solvothermal reactions of lanthanide salts with two types of flexible substituent adipates. All of these CPs were characterized by single‐crystal X‐ray diffraction, elemental analysis, IR spectroscopy, powder X‐ray diffraction, and thermal analysis. Structural analyses reveal that CPs 1–6 and 7–12 are isostructural, respectively. CPs 1–6 show a two‐dimensional (2D) layer constructed from the 3‐methyl‐adipate anions bridging two types of binuclear Ln2 units. The adjacent 2D layers are further extended into a three‐dimensional (3D) supramolecular framework through the hydrogen‐bonding interactions. CPs 7–12 also exhibit a 2D structure. The carboxyl groups of 3‐tert‐butyl‐adipate link four types of TbIII ions to form a one‐dimensional (1D) inorganic TbIII chain. The neighboring 1D inorganic TbIII chains are further connected by the 3‐tert‐butyl‐adipate anions to construct a 2D network. The effect of substituent groups on the formation of adipate‐based lanthanide CPs as well as the photoluminescence and magnetic properties of 1–12 were investigated in detail.

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Coordination polymers of lanthanide complexes with benzene dicarboxylato ligands

Cited by 25 publications

References 41 publications

Hexanuclear Molecular Precursors as Tools to Design Luminescent Coordination Polymers with Lanthanide Segregation

Hexanuclear Molecular Precursors as Tools to Design Luminescent Coordination Polymers with Lanthanide Segregation

Lanthanide Contraction in Action: Structural Variations in 13 Lanthanide(III) Thiophene-2,5-dicarboxylate Coordination Polymers (Ln = La–Lu, Except Pm and Tm) Featuring Magnetocaloric Effect, Slow Magnetic Relaxation, and Luminescence-Lifetime-based Thermometry

Two Series of Substituent‐Group‐Directed Adipate‐Based Lanthanide Coordination Polymers: Syntheses, Structures, Photoluminescence, and Magnetism

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