Multi-functional magnetic, ferroelectric, and fluorescent homochiral lanthanide (Ln)–camphorate compounds built on helical {Ln–O}n inorganic substructures

Song, Yu‐Mei; Huang, Hongfeng; Sun, Gong-ming; Liao, Zhen-wei; Luo, Mingbiao; Liu, Shujuan; Luo, Feng

doi:10.1039/c1ce05604b

Cited by 22 publications

(10 citation statements)

References 28 publications

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“…4(i). Although a few hex-net LOFs are known (Cao et al, 2014;Chen, Hu et al, 2016;Liu, Li et al, 2014;Lü et al, 2008;Smith et al, 2016;Song et al, 2011), to the best of our knowledge, the present 3D hydrogen-bonded hex-net chiral LOF built from achiral ligand is unprecedented. Furthermore, hydrogenbonding interactions between the nitro groups and the related aromatic H atoms also make key contributions to the stabilization of the resulting 3D structure [C16Á Á ÁO2 iv = 3.061 (5) Å and C16-H16AÁ Á ÁO2 iv = 121 ; C31Á Á ÁO6A vi = 3.058 (6) Å and C31-H31AÁ Á ÁO6A vi = 141 ] (Table 2).…”

Section: Tablementioning

confidence: 95%

Unprecedented three-dimensional hydrogen-bonded hex topological chiral lanthanide–organic frameworks built from an achiral ligand

Qin¹,

Feng²,

Yang³

et al. 2018

Acta Crystallogr C

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The design and preparation of chiral metal–organic frameworks (CMOFs) from achiral ligands are a big challenge. Using 3‐nitro‐4‐(pyridin‐4‐yl)benzoic acid (HL) as a new linker, a total of eight chiral lanthanide–organic frameworks (LOFs), namely poly[diaquatris[μ2‐3‐nitro‐4‐(pyridin‐4‐yl)benzoato‐κ2O:O′]lanthanide(III)], l‐ and d‐[Ln(C12H7N2O4)3(H2O)2]n [(1), Ln = Eu; (2), Ln = Gd; (3), Ln = Dy; (4), Ln = Tb], were hydrothermally synthesized without chiral reagents and determined by X‐ray crystallography. Crystal structure analyses show that l‐(1)–(4) crystallize in the hexagonal P65 space group and are isomorphous and isostructural, while the enantiomers d‐(1)–(4) crystallize in the hexagonal P61 space group. All LnIII ions are octacoordinated by six carboxyl O atoms of six 3‐nitro‐4‐(pyridin‐4‐yl)benzoate ligands and two water molecules in a dodecahedral geometry. A one‐dimensional neutral helical [Ln2(CO2)3]n chain is observed in (1)–(4) as a chiral origin. These helical chains are further interconnected via directional hydrogen‐bonding interactions between pyridyl groups and water molecules to construct a three‐dimensional (3D) homochiral network with hex topology. The present CMOF structure is the first chiral 3D hydrogen‐bonded hex‐net and shows good water stability. Solid‐state circular dichroism (CD) signals revealed that (1)–(4) crystallized through spontaneous resolution. Furthermore, (1) and (4) display a strong red and green photoluminescence at room temperature, respectively, but their intensities reduce to almost half at 200 °C. Notably, upon excitation under visible light (463 nm), a circularly polarized luminescence (CPL) of (1) in the solid state is observed for the first time, with a glum value of 2.61 × 10−2.

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Section: Tablementioning

confidence: 95%

Unprecedented three-dimensional hydrogen-bonded hex topological chiral lanthanide–organic frameworks built from an achiral ligand

Qin¹,

Feng²,

Yang³

et al. 2018

Acta Crystallogr C

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“…2 (a) A view along the c direction of the helical substructure of {Gd(COO) 3 } n and {Gd-O} n ; (b) A view of the special hex rod-packing architecture built on the helical {Ln-O} n rod substructure. (Reproduced from Song et al [55] by permission of The Royal Society of Chemistry) combination of an enantiopure D-cam ligand with an achiral bdc ligand brings both homochirality and rigidity into the lanthanide MOFs materials. The crystal structures of these MOFs reveal that they are isostructural and crystallize in orthorhombic, chiral space group P2 1 2 1 2 1 .…”

Section: Synthesis Of Chiral Lanthanide Mofs With Chiral Ligandsmentioning

confidence: 98%

“…Song et al [55] have first constructed homochiral lanthanide-based chiral MOFs, [Ln(μ-H 2 O)(D-cam)(CH 3 COO)] n (Ln ¼ Gd, Tb, Eu, Dy), by using enantiopure D-camphorate ligand (D-H 2 cam) and Ln(CH 3 COO) 3 under hydrothermal condition. These isomorphous Ln(III)-camphorate compounds with the P6 5 chiral space group.…”

Section: Synthesis Of Chiral Lanthanide Mofs With Chiral Ligandsmentioning

confidence: 99%

Chiral Lanthanide Metal-Organic Frameworks

Liu

Tang

2014

Structure and Bonding

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Chiral metal-organic frameworks (MOFs) have attracted much attention, not only due to their potential applications in enantioselective separation and catalysis, but also because of many advantages such as the high density of active catalytic centers, high level of porosity, regular and reliable crystalline nature, and relatively easy immobilization as compared to other heterogeneous systems. As metal-connecting nodes of MOFs, a large number of chemical synthetic strategies have focused on the transition metal ions which exhibit specific coordination geometries and restricted stereochemistry in the past two decades. However, the researches on chiral lanthanide MOFs are still limited up to now because of high coordination numbers, kinetic lability, weak stereochemical preference, and more variable nature of the coordination sphere for lanthanide ions. In this chapter, we would give a brief introduction to highlight the synthetic approaches reported and the structural features of chiral lanthanide MOFs or coordination polymer, which may be beneficial to explore structurally and functionally defined chiral solid materials.

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“…In the field of molecule-based magnets, the lanthanide(III) ions in MOFs and CFs, especially the Dy 3+ ion, can exhibit superparamagnetic properties thanks to not only significant magnetic anisotropy but also large magnetic moments, , such as single-molecule magnet (SMM) properties that make LnCPs and LnMOFs potential applications in the fields of information storage and molecular device. However, owing to the characteristics of ferroelectricity , and nonlinear optical activity, the chirality in molecular materials is highly valued, which is especially beneficial for multifunctional integration; − moreover, homochiral MOFs may be used in not only heterogeneous asymmetric catalysis but also enantioselective separation. − However, it remains a great challenge to obtain homochiral MOFs or homochiral CPs, − especially homochiral LnCPs or homochiral LnMOFs. − …”

Section: Introductionmentioning

confidence: 99%

“…So far, most of the reported homochiral LnCPs or homochiral LnMOFs are obtained by solvothermal technology, − which requires high energy consumption and often acquires racemates under high temperature and high pressure conditions. Therefore, it is necessary to investigate the room temperature synthesis of homochiral LnCPs or homochiral LnMOFs under normal pressure.…”

Section: Introductionmentioning

confidence: 99%

Enantiopure Chiral Two-dimensional Sinusoidal Lanthanide(III) Coordination Polymers Based on R-/S-2-Methylglutarate: Luminescence, Magnetic Entropy Change, and Magnetic Relaxation

Liu

Zhang

Hao

et al. 2019

Crystal Growth & Design

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As a base for neutralizing homochiral dicarboxylic acids [R-/S-2-methylglutaric acid, abbreviated as (R/S)-2-MG] rather than an N-donor ligand, 1,3-di(4-pyridyl)propane participates in the self-assembly of isostructural, homochiral lanthanide(III) coordination polymers derived from (R/S)-2-MG at room temperature, which show 2D sinusoidal ruffling (4, 4) network structures with the formulas {). Among them, the europium(III) and terbium(III) compounds show solid fluorescent properties characteristic of lanthanide(III) ions, while the dysprosium(III) compound may exhibit magnetic relaxation. Furthermore, the magnetic entropy change or magnetocaloric effect of the gadolinium(III) complex is studied.

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Multi-functional magnetic, ferroelectric, and fluorescent homochiral lanthanide (Ln)–camphorate compounds built on helical {Ln–O}n inorganic substructures

Cited by 22 publications

References 28 publications

Unprecedented three-dimensional hydrogen-bonded hex topological chiral lanthanide–organic frameworks built from an achiral ligand

Unprecedented three-dimensional hydrogen-bonded hex topological chiral lanthanide–organic frameworks built from an achiral ligand

Chiral Lanthanide Metal-Organic Frameworks

Enantiopure Chiral Two-dimensional Sinusoidal Lanthanide(III) Coordination Polymers Based on R-/S-2-Methylglutarate: Luminescence, Magnetic Entropy Change, and Magnetic Relaxation

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