2-Chloro-5-nitrobenzoato complexes of Eu(III) and Tb(III) – A 1D coordination polymer and enhanced solution luminescence

Viswanathan, Subha; Bettencourt‐Dias, Ana de

doi:10.1016/j.inoche.2006.01.022

Cited by 26 publications

(9 citation statements)

References 32 publications

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“…Similar work with a thiophene-derivatized isophthalic acid, 5-(thiophen-3-yl)isophthalic acid (Figure ), led to the formation and isolation of two-dimensional coordination polymers . Coordination polymers are frequently encountered when carboxylates are present in a ligand, ,− and while we have not seen their formation with the thiophene-functionalized nitrobenzoic acids, the presence of the two carboxylate functional groups in the thiophene-functionalized isophthalic acid facilitated their formation. The two-dimensional coordination polymers isolated in this case (Figure a) extend along the b axis, with the layers of two sheets interacting through hydrogen bonds of the thiophene ring H atoms with the water molecules bound to the metal ions of the adjacent sheets (Figure b).…”

Section: Results and Discussionsupporting

confidence: 58%

Ligand Design for Luminescent Lanthanide-Containing Metallopolymers

Bettencourt‐Dias

Rossini

2016

Inorg. Chem.

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The isolation of emissive materials with lanthanide ions is a topic of interest for imaging, display, and sensing applications, and it requires tuning of the electronics of the systems, such that, during the process of sensitization of the metal-centered luminescence, energy transfer from the sensitizer to the lanthanide ion is efficient and the resulting materials have the characteristics required for a given application. We discuss here our group's work in controlling the singlet- and triplet-state energies of sensitizing ligands through the choice of functional groups on the pyridine rings chelating to the lanthanide ions and show how we achieved progressively higher emission efficiencies. We describe targeted functionalization that led to highly emissive systems in solution and in the solid state and to new metallopolymers with norbornene or dicyclopentadiene-based backbones and pyridinebis(oxazoline) pendants, which display red Eu-based, green Tb-based, and, for the first time, blue Tm-based emission.

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Section: Results and Discussionsupporting

confidence: 58%

Ligand Design for Luminescent Lanthanide-Containing Metallopolymers

Bettencourt‐Dias

Rossini

2016

Inorg. Chem.

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“…Our research in sensitized luminescence of Ln III ions, − prompted us to screen as an antenna dpat . This ligand, which is N 2 , N 2 , N 4 , N 4 , N 6 , N 6 -hexakis(pyridin-2-ylmethyl)-1,3,5-triazine-2,4,6-triamine, was reported by Maheswari and co-workers; it forms a Zn complex with displays an anion-π interaction between the nitrate anion of a [Zn(NO 3 ) 2 ] moiety with the triazine ring .…”

Section: Introductionmentioning

confidence: 99%

Anion-π and H-Bonding Interactions Supporting Encapsulation of [Ln(NO₃)_6/5]^3–/2– (Ln = Nd, Er) with a Triazine-Based Ligand

2019

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Reaction of NdIII and ErIII nitrate salts with a 1,3,5-tris(dipicolylamine)-triazine (dpat) ligand yielded two unprecedented examples of [Ln(NO3)6/5]3–/2– (Ln = Nd, Er) moieties completely encapsulated by the ligands. They are found in the two new complexes, [(H3 dpat)2][(Nd(NO3)6)2]·2CH3CN (1), and the related [(H3 dpat)2][(Er(NO3)5)3]·3CH3CN·2H2O (2). The structures of the complexes are similar and they crystallize in the triclinic P-1 space group with a = 12.1630(3), b = 12.2694(3), c = 17.6357(5) Å, V = 2611.10(12) Å3, and a = 14.3372(4), b = 17.1271(4), c = 25.2207(7) Å, V = 5934.7(3) Å3, respectively. Anion-π interactions, which are reported here for the first time for LnIII ion complexes, hydrogen bonding interactions and π–π stacking support the formation of the encapsulated species. Evidence of the protonated dpat ligand in 1 and 2 was found through isolation of (H2 dpat)(NO3)2. Finally, the pH-dependent ability of the ligand to extract LaIII and nitrate ions from aqueous into toluene solution is demonstrated.

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“…De Bettencourt Dias and co-workers were the first to report any sensitized Ln 3+ emission with a nitrated aromatic ligand, 4‑nitro‑3‑thiophen‑3‑yl benzoic acid . Since then, there have been several reports of sensitized Ln 3+ emission with nitrated ligands including other benzoates, − salicylates, oxyquinolates, anthranylates, pyridines, and salicylaldehydes, and even enhancement of Eu 3+ emission with some nitrated salicylate and oxyquinolate over benzoate ligands …”

Section: Introductionmentioning

confidence: 99%

Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln³⁺ Emission

et al. 2021

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Reported are the syntheses, crystal structures, and photophysical properties of 28, novel lanthanide compounds across five structural types, [Ln(3-NO2Tp)2(NO3)] (1-Ln, Ln = La–Tm, except Pm), [Bu4N][Ln(3-NO2Tp)(NO3)3] (2-Ln, Ln = Yb, Lu), [Eu(3-NO2Tp)2Cl(H2O)]·2 i PrOH (3-Eu), [{Ln(3-NO2Tp)2}2(μ2-CO3)]·MeOH (4-Ln, Ln = La–Gd, except Pm), and [{Ln(3-NO2Tp)}4(μ2-OMe)6(μ4-O)] (5-Ln, Ln = Pr–Tb, except Pm) with the 3-nitrotrispyrazolylborate (3-NO2Tp–) ligand. The reaction of methanol or isopropanol solutions of LnX3 (X = Cl, NO3) with the tetrabutyl ammonium salt of the flexidentate 3-NO2Tp– ([Bu4N][3-NO2Tp]) yields Ln(3-NO2Tp) x complexes of various nuclearities as either monomers (1-Ln, 2-Ln, 3-Eu), dimers (4-Ln), or tetramers (5-Ln) owing to the efficient conversion of atmospheric CO2 to CO3 2– (dimers) or ligand controlled solvolysis of lanthanide ions (tetramers). 3-NO2Tp– is an efficient sensitizer for both the visible and near-IR (NIR) emissions of most of the lanthanide series, except thulium. Optical measurements, supported by density functional theory calculations, indicate that the dual visible and NIR Ln3+ emission arises from two intraligand charge transfer (ILCT) transitions of 3-NO2Tp–. This is the first report of lanthanide complexes with a nitro-functionalized pyrazolylborate ligand. The derivatization of the known Tp– ligand results in new coordination chemistry governed by the increased denticity of 3-NO2Tp–, imparting remarkable structural diversity and charge transfer properties to resultant lanthanide complexes.

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2-Chloro-5-nitrobenzoato complexes of Eu(III) and Tb(III) – A 1D coordination polymer and enhanced solution luminescence

Cited by 26 publications

References 32 publications

Ligand Design for Luminescent Lanthanide-Containing Metallopolymers

Ligand Design for Luminescent Lanthanide-Containing Metallopolymers

Anion-π and H-Bonding Interactions Supporting Encapsulation of [Ln(NO₃)_6/5]^3–/2– (Ln = Nd, Er) with a Triazine-Based Ligand

Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln³⁺ Emission

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2-Chloro-5-nitrobenzoato complexes of Eu(III) and Tb(III) – A 1D coordination polymer and enhanced solution luminescence

Cited by 26 publications

References 32 publications

Ligand Design for Luminescent Lanthanide-Containing Metallopolymers

Ligand Design for Luminescent Lanthanide-Containing Metallopolymers

Anion-π and H-Bonding Interactions Supporting Encapsulation of [Ln(NO3)6/5]3–/2– (Ln = Nd, Er) with a Triazine-Based Ligand

Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln3+ Emission

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Anion-π and H-Bonding Interactions Supporting Encapsulation of [Ln(NO₃)_6/5]^3–/2– (Ln = Nd, Er) with a Triazine-Based Ligand

Structural Diversity of Lanthanide 3-Nitrotrispyrazolylborates: Tunable Nuclearity and Intra-Ligand Charge Transfer Sensitization of Visible and NIR Ln³⁺ Emission